Т е еп Т. Т. М.

К iМVA Kitapligx
N e .i ____________

г л
P R E FA C E

O v e r tw o y ears o f w o rk h a v e go n e into a carefu l re v isio n based o n the ex p e rie n c es o f

o u r o w n teach in g and th e su g g estions and id eas o f o u r m any u sers and colleag u es. D uring
th e rev isio n w e h a v e tried to m ak e the te x t m o re in terestin g and read ab le, b u t w e retained
th e sam e cle a r d iscu ssio n and ch aracteristics o f the previous editions. W e are ex cited about
th is n ew e d itio n o f o u r bo o k. W e h o p e th at stu d en ts and o u r c o lleag u es sh are o u r e x c ite ­
m ent.
W e h a v e also p re p a re d th e b o o k s e x p e r im e n ts fo r c h e m istr y and te a c h e r 's m a n ­
u a l fo r c h e m is tr y I .
W e sincerely appreciate all the sta ff fo r their helpful suggestions and com m ents.
C h e m istry is o n e o f th e im p o rtan t b ran c h es o f scien ce and it d eals w ith all o f the su b ­
stan ces m a k in g u p o u r en v iro n m en t. T h e stu d y o f c h em istry m a k e s the stu d e n ts fam iliar
w ith the th in g s o ccu rrin g around us.
T h is te x tb o o k w as d e sig n ed fo r a one y e a r c h em istry course. T h e tex t is a p p lica b le to
h ig h sch o o ls at w h ic h E n g lish is tau g h t as a second language. A t the end o f this course, the
students w ill lc a m the co n cepts and principles o f ch em istry and they w ill b e able to share in
the ex citem en t o f chem istry.
In w ritin g th is b o o k , w e c o n sid e red so m e facts to m o tiv ate o u r stu d e n ts an d tu rn in g
them o n chem istry. T o h eig hten students interest and to m ake chem istry enjoyable :
(1) E xtrem e care h a s b een taken to provide clear, con cise explanations o f to p ics th at use
a clear, und erstan d ab le language.
(2) M a rg in n o te s an d fig u res are u sed to e m p h a siz e and reco g n iz e so m e im p o rta n t
p o in ts.
(3) N ew term s are se t in black boldface type w hen th ey are defined first.
(4) A short g lossary is g iv en at the end o f each ch ap ter to em p h asize new term s included
in the chapter.
(5) A larg e n u m b e r o f w o rked-out exam ples follow ed im m ediately by exercises w ith an ­
sw ers is given to d ev elo p pro b lem -so lv in g technique.
( 6 ) E n d -o f-c h a p te r e x e rc ises are d iv id e d into q u e stio n s (w h ic h req u ire v erb al an w ers)
and p roblem s.
(7) A s e lf test c o n sistin g 2 0 m u ltip le ch o ice q u estio n s is in ten d ed to b e u sed in d e p e n ­
d en tly b y stu d en ts after stu d y in g ea ch chapter. A nsw ers to s e lf tests are g iv en at th e
en d o f th e book.
( 8 ) M o re challenging problem s are m arked w ith asteriks.
W e b eliev e th at th e b o o k is n o t th e b est b u t it is, w e expect, the m o st u se fu l and h elp fu l
o n e at hand fo r b o th instructors and students to im prove ch em istry program in T urkey.
H elpful suggestions and com m ents for the im provem ent o f this book w ill be w elcom ed.

The Authors
4i -j
 CONTENTS V

1 . AN E X P E R IM E N T A L S C IE N C E : C H E M IS T R Y 3

1.1 W hat is C hem istry .......................................................................................................................3

1.2 M easurem ents and U nits ................................................. ,...................... 3
1.2.1 L ength ............................. .'................................................................................................. 4
1.2.2 M ass .......... 5
1.2.3 V olum e r.................... — — v.....................................■■■■-5
1.2.4 T em perature ..................................................................................................... 6
1.3 U ncertainty in Science ................................................................................................................. 8
1.3.1 S ignificant Figures ..................... 8
1.3.1.1 Significant Figures in M athem atical Operations .......................................................9
1.3.2 Scientific N otation ......................................................................................................... 11
1.4 Comm on Properties o f M atter ..................................................................................................15
1.5 C haracteristic Properties o f M ailer ........................................................................................... 15
Som e New T erm s .................................................................................................................................. 20
R eview Q uestions ................................................. 21
R eview P roblem s .................................................................................................................................... 21
S elf T est .................................................................................................................................................... 22

2. A S C IE N T IF IC M ODEL :A T O M IC THEORY ................................................. 25

2.1 C lassification of M atter ................ 27

2.1.1 Pure Substances ........................................................ 27
2.1.2 M ixtures ....................................................................... 28
2.2 Sym bols and Form ulas ................................................................................................... 30
2.2.1 Sym bols ............................................................................................................................. 31
2.2.2 Form ulas ............................................................................................................................32
2.3 C hem ical N om enclature ......... 34
2.3.1 U sing V alence Rules to W rite Form ulas .................................................................34
2.3.2 N am ing C hem ical C om pounds ..................................................................................36
2.3.2.1 M etal - N onm etal Com pounds ......................................................................... 36
2.3.2.2 N onm etal - N onm etal Com pounds ............ 39
2.4 R elative A tom ic W eights .........................................................................................................40
2.5 M ole Concept and Avogadro's N um ber ................................................................................ 40
2.5.1 A tom ic M ass or Atomic W eight ............................................................................... 43
2.5.2 M olecular W eight ...........................................................................................................45
2.5.3 M olar V olum e ............... 47
2.6 Integration o f M ole C oncept ................................................................................... 48
f 2.7 A tom ic W eight D eterm ination ................................................................................................ 49
2.8 Percentage Com position of C om pounds .................................................................................53
2.9 D erivation o f Em pirical Form ulas ........................................................................................... 54
Som e N ew T erm s ......;..................................................... 57
R eview Q u estio n s .......................................................... 58
R eview P roblem s .................................................... 58
S elf T est ...................................................................................... 62

3 . THE G A SEO U S S T A T E O F M A TTE R .............................................................................65

3.1 G eneral Properties o f G ases ...................................................................................................... 67

3.1.1 P ressure ............................................................. 67
3.1.1.1 U nits of Pressure ................................................................................................ 67

X .’ . - ........ ’ ’
 VI
CONTENTS
3.1.1.2 M easuring Pressure ................................................................................ 6Я
3.1.2 -K in etic Theory of G ases...............................................................................................71
3.1.3 G raham 's Law o f D iffusion........................................................................................7-1
3.2 G as Law s ................................................................................ 73
3.2.1 A vogadro’s Law .............................................................................................................73'-.
3.2.2 B oyle's Law ............................................................................................................... >. 75
3.2.3 C harle's Law ......................................................................................................... 76
3.2.4 Gay Lussac's Law ...................................................................................................... ..*78
3.2.5- Ideal Gas Law ................................................................................................................78
3.3 Gas M ixtures and Partial Pressure ..........................................................................................85
3.4 C ollecting G ases Over W ater ...................................................................................................88
Som e New Term s .............................................................................................................................. 91
R eview Q uestions ...............................................................................................7........................... 91
R eview P roblem s ...................... 92
S elf T est ................................................................................................................................................ 100

4. C H E M IC A L R E A C T IO N S .................................. 103

4.1 Physical and Chem ical Changes .......................... 105

4.1.1 Physical C hanges ...................................................................................................... 105
4.1.2 C hem ical C hanges ......................................................................................................105
4.2 C hem ical E quations ...................................................................... 107
4.2.1 W riting Chem ical Equations ................................................................................... 107
4.2.2 Balancing Chcrni 1 F 'nations ............................................................................. 107
4.3 Types of C hem ical Reactions ............................................................................................... 110
4.4 C alculations Based on Equations .............................................................................................I l l
4.4.1 Calculations About Quantities of Reactants and P ro d u c ts.................................. I l l
4.4.2 R eactions Involving Lim iting R eagents................................................................. 115
4.4.3 R eactions Involving Impure Sublances ............................................................... 119
4.4.4 C onsecutive R eactions .............................................................................................121
4.4.5 S im ultaneous R eactions............................................................................................ 123
4.4.6 D eterm ining Em pirical F orm ula...............................................................................124
4.4.7 A tom ic W eight D eterm ination.............................................................................. 125
4.4.8 Pressure V olum e Changes in Reactions .................................... 126
4.4.9 Calculations About Gases Collected Over W a te r ................................................... 128
Som e New Term s .......................................................................................................................... 129
R eview Q uestions .............................................................................................................................129
R eview Problem s .......................................................................................................... 130
S elf T est ......................................................................................................................................... 138

5. CO N D EN SED PH A SES O FM ATTER: L IQ U ID S AND S O L ID S .................... 141

5.1 P hase Changes ...... :......................................................................................................................143

5.1.1 M elting and Heat of M elting .................................................................................. 143
5.1.2 Evaporation and H eat of Evaporation ........................ 145
5.2 Vapor Presurre and B oiling Point ................................ 148
5.3 S olutions .....................................................................................................................................150
5.3.1 Properties o f Solutions ........................................................................................... 151
5.3.2 C oncentrations o f Solutions .................................................................................... 153
5.3.2.1 Percentage C oncentration ........................................... .-.................................... 153
5.3.2.2 M olar C oncentration (M olarity) .................................................................... 156
5.3.3 D ilution .......................................................................................................................... 159
 vn
CONTENTS
5.3.4 M ixing Solutions .........................................................................................................160
5.3-5 Chem ical R eactions in Solutions ............................................................................161
5.3.6 Equivalent W eight and N orm ality ........................................................................ 162
5 - Solubility .................................................................................................................................... 165
5.4.1 Separations of Solutions into Their Components ................................................ 167
- 5 Electric Nature o f M atter and Ionic Equations .....................................................................168
5 j6 loo C oncentration ........................................................................................................................ 169
5 ~ S olubility R u les............................................................................................................................. 171
5 5 P recipitation Reactions..... ............................................................................................................ 172
s i c e New T erm s ........................ 175
Review Q uestions ........................................................................................ 175
B n i e w P roblem s ...................................................... 176
5: . Te>: ' ........... 184

r A T O M IC STRU CTU RE AND C H E M IC A L P E R IO D IC IT Y ............................. ] 87

6Л C hem ical Evidences for Atoms ..................................................................................................189

6.1.1 Law of D efinite Proportions ................... .............................................................. 189
6.1.2 Law o f M ultiple Proportions ................................................................................ 191
6.1.3 Law o f Com bining Volumes .................................................................................. 193
6.1.4 Chemical Evidence for the Electrical Nature of M atter : Faraday's Laws ..............194
- I Eha-iging C oncepts o f Atom ................................................................................................. 198
т 2.1 D iscovery of Electron ...............................................................................................199
^ 2.2 D iscovery of Proton ...................... 199
6-2.3 Thom son's A tom ic Model .....................................................................................200
6_2 4 R utherford's A tom ic Model ......................................... 200
6-2-5 D iscovery o f N eu tron ..................................................................................................201
■22 ~ Atomic Num ber and Atomic Mass N um ber............................................................202
6 2 “ Isotopes ............................................................................ 204
t * Bofcr > V.omic M odel ...................................................................2........................................... 206
6 5 '. L ight ................................................................. 206
6-3-2 A tom ic Spectrum ........................................ 207
6 3 3 The Bohr M odel o f A tom .......................................................................................... 208
6 .4 » i - : M echanics and M odern Atomic Theory.......................................................................211
- - . Shortcom ings of Bohr's Atomic M odel................................................................... 211
• -2 M odem A tom ic T heory .............................................................................................. 211
- - : Q uantum N um bers.............................................. *................................................212
6 lS П и — C o n fig u ratio n..................... 214
* * ЛишиЬс T able ..............................................................................................................................218
ii Electronic Structure and Periodic Table ................................................................. 220
t..f.2I —т а . " ; Period and G roup Num ber .........................................................................220
I ta a a B c f to p e ru e s ...................................... 222
ftli Л&звас Radius ............................................................................................................. 222
i. ~2! Ъавыаах® Energy ...................................................... 224
6 J 3 О б а Periodic Properties ....................................................... 228
S o a e Чэт» Т я и * ......... 231
i 2.-2
В в н в в M bM e b i ................ 233
Ш Ш U rn .................................. 23S
 VIII
CONTENTS
7. SO M E S E L E C T E D F A M IL IE S IN THE P E R IO D IC T A B L E .......................... 241

7.1 Periodic Properties ..................................................................................................................... 243

7.2 N oble G ases ............................................................................................................................... 243
7.3 A lkali M etals ................................................................................................................................ 244
7.3.1 O ccurrence and Preparation .............................. 244
7.3.2 Com pounds and Reactions of Alkali M etals ...........................................................245
7.4 H alogens .................................. .-......... 247
7.4.1 O ccurrence and Preparation ..................................................... 248
7.4.2 C hem ical Properties ......................................................................................................249
7.5 Hydrogen : A Fam ily by Itself ................................................................................................ 251
Som e New Term s ................................................. 252
R eview Q uestions ................................... 252
R eview Problem s ............................................. 253
S e lf T est .................................................................................................................................................. 254

8- NUCLEAR C H E M IS T R Y ......................... 257

8.1 The Structure o f the N ucleus ................................................................................................. 258

8.2 R adioactivity .................................................................................................... 258
8.2.1 Types o f R adioactive Decay ............. 259
8.2.1.1 Alpha R adiation >..................................... 259
8.2.1.2 Beta R adiation ............. 260
8.2.1.3 G am m a Rays ....................................................................................................261
8.2.1.4 Positron Em ission .........................................................................................261
8.2.1.5 N eutron Em ission ............................................................................................... 261
8.2.1.6 E lectron C apture .................................................................................... 261
8.2.2 N atural and Artifical Radioactivty ...........................................................................262
8.3 Rate o f R adioactive Decay ....................................................................................................263
8.4 N uclear R eaction ...................................................................................................................... 266
8.4.1 The Energy Involved in Nuclear Reactions ............................................................268
Som e New T erm s ......................„ ........................................................................................................270
R eview Q uestions .............................................................................................................. 270
R eview Problem s ................................................................................................. 270
S e lf T est .................................................................................... 274
A nsw ers To The Self Tests ............................................................................................................. 276
 CHAPTER

An Experimental Science : Chemistry

The objectives of this chapter are to enable the student to :

1. Define chemistry, matter, energy, and observation.

2. State the basic units of mass, length, and volume in the
metric system.
3. Explain and compare temperature scales.
4. Become fam iliar with the concepts of u n c e rta in ty in
s c ie n c e .
5. State the number of significant figures in a numerical
q u a n tity .
6. Express the result of a calculation with the appropriate
number of significant figures.
7. Change the decimal numbers into exponential forms or
change the exponential numbers into the decimal numbers.
8. Become fam iliar with the characteristic properties of
m atter.
 An Experim ental Science : Chem istry 3

T h o s e s c ie n c e s a re v a in 1.1 WHAT IS CHEMISTRY ?

and full o f e rro rs w h ich are C hem istry, p h y sics, b iology and ea rth science are the fo u r m a in bran ch es
n o tb o rn fro m e x p e rim e n t
o f na tu ra l sciences. E ac h o f the b ra n ch es o f n atu ral scien ce has its o w n area
•the m o th e r o f all c ertain ty
th a t is c lo se ly related to o th e r b ran ch es o f n atu ral science. N o b ra n c h o f
L E O N A R D O da V inci science can be entirely independent o f the others. T herefore, scientists m ust be
ab le to c o m m u n ic a te w ith one an o th er. B io lo g ists m u st b e ab le to ta lk to
ch em ists, and chem ists m u st be able to talk to p h y sicists. S cien tists d ea lin g
w ith natural science use com m only the sam e m ethods fo r th eir researches, o b ­
servations and experim ents.
In th is book, w e are g o ing to stu d y the su b ject o f chem istry : C h em ical
P r in c ip le s and C o n c e p ts.

What is an experiment? C h em istry is the science that deals with the composition and structure o f
m atter and with the changes m atter undergoes. It is also co n ce rn e d w ith the
An experimental work may p ro p erties o f su b stances and w ith th e ir en erg y re la tio n sh ip s . E n er g y is d e­
be organized as follows:
(1) P r o b l e m: W hat ques­
fin e d as the ability to do work. It e x ists in m an y d iffe re n t fo rm s, e a c h o f
tion do you want to answer in w h ic h m ay b e c h an g ed in to any o f the o th e r fo rm s. H eat, lig h t, m o tio n ,
performing experiment. sound and electricity are fam iliar form s o f energy.
(2) P r o c e d u r e : W hich
steps should you follow in do­ A n ex p erim ent is a controlled situation to see if the co nclusions deduced
ing experiment. from a natural law agree w ith actual experience. A ll th at chem ists have learned
(3) Observation: What do
is based o n the results o f experim ents. F undam ental law s o f ch em istry accept­
you see, smell or hear.
(4) C o n c l u s i o n : W hat is ed to d ay w ere obtained by ex p erim ents. In ad d itio n w e m ay m ak e m an y o b ­
your answer to the question. serv atio n s o f a pro b lem before w e h av e designed co n trolled ex p erim en ts. A n
o b s e r v a tio n is som ething w e actually see, hear or feel.

1.2 MEASUREMENTS AND UNITS I

T h e reliable know ledge is obtained by laboratory experim ents. I f an exper­
im en t is d o n e, you are alw ays su p p o sed to m ak e m e a su re m e n ts. B e ca u se
m e a su re m e n ts are im p o rtan t in co m m u n icatin g w ith o th e r p eo p le. T h e m o st
co m m o n m e a su re m e n ts you w ill ro u tin ely ca rry o u t in th e c o u rse o f y o u r
sc ie n tific stu d ie s a re le n g th , m a ss, v o lu m e and t e m p e r a t u r e . In o u r
m e a su re m e n ts in ch em istry lab o rato ries, w e w ill, in g eneral, u se th e m e tr ic
sy stem . T h e m e tric system o f m e asu re m e n t is u sed in all sc ien tific studies.
T he m etric units have the advantages o f
(a) they are based on a decim al system that m akes conversion to m any differ­
ent units by shifting the decimal point.
(b) these units are standard among scientists in every part o f the world.
T h e m o d e m form o f th e m etric system is called the In te r n a tio n a l S y s­
te m o f U n its o r SI. T h e In ternational S ystem is fo unded o n sev en b ase units
and tw o su p p lem en ta ry . (See T a b le 1.1)
4 Chapter 1

T A B L E 1.1 Base Units and Supplem entary Units o f S I

f Physical Property Name of Unit Symbol Л

Length Meter m
Mass Kilogram kg
Time Second s
Electric current Ampere A
Temperature Kelvin К
^ Quantity of substance Mole mol

1.2.1 LE N G T H
T h e SI b ase u n it fo r length is the m eter (m ). O ne m eter is defined as one
ten-millionth o f the distance fro m the equator to the North Pole. T he new defi­
n itio n o f the m e te r is 1650763.73 w avelengths o f th e oran g e-red lin e o f k ry p ­
to n - 86 .
M u ltip liers o r fractions o f base units are indicated b y the u se o f prefixes.
(S ee T ab le 1.2).
T A B L E 1.2 D ecim al M u ltip liers th a t Serve as S I U nit P refix
r Prefix Symbol Factor N

Giga G- 1 000 000 000 = 10 9

Mega M- 1 000 000 = 106
Kilo k- 1 000 = 103.
Hecto h- 100 = 102
Deca da- 10= 101
BASE UNIT
deci d 0.1 = 1 0 '1
centi с 0.01 = 10'2
milli m 0.001 = № 3
micro h 0.000 001 = 10‘6
nano n 0.000 000 001 = 10‘9
ч Pico P 0.000 000 000 001 = 10*'12
J
T h e base u n it o f length, the m eter (m ), is n o t used to record the distances
b etw een cities. Instead, a larg er unit, the kilo m eter (km ) is m ore convenient.
1 km = 1 000 m =10 000 dm = 100 000 cm = 1000 000 m m .

EXAMPLE 1.1 C o n v e r sio n o f U n its in L e n g th

Problem : Change the following units of length using Table 1.2
a )T k m = m, b) 2 hm =....dm,c) 4 dm = mm, d) 4800 cm = . dam,
e) 3006 mm = hm, 0 3600 m = ...... km.
Solution : a) 3000 b) 2000 c) 400 d) 4.8 c) 0.03 0 3.6

EXERCISE 1.1 Which number should replace the question mark in each of the following?
a) 400 km =? m b) 50 m =? mm c) 4 dam = ? cm
d) 8 cm =? m e) 60 mm =? dm 0 W00 p m = ? cm .
 An Experim ental Science : Chem istry 5
1 .2 .2 MASS
M a ss is the quantity o f m atter p rese n t in a m aterial body . T h e
m ass o f a b o d y is c o n sta n t and is in d e p e n d en t o f lo catio n . T h e term s
m a s s and w e ig h t are o fte n u se d in te rc h a n g e ab ly . In fac t, th e tw o
term s re fe r to d iffe ren t th in g s. W eig h t is a m easure o f the fo r c e or
pull o f gravity o f an object. T he w eight o f an object is m easured w ith a
sp rin g scale, b u t m ass m ay be m easu red b y an eq u al-arm b alan ce. See
F ig u re 1.1.
In the SI, the base u n it fo r m ass is th e k ilo g ra m (k g). H o w e v ­
-ф ; : ~%r er, the gram (g), is a m o re co n v e n ien t fo r m o st lab o rato ry m e a su re ­
FIGURE 1.1 Determi ni ng m ents. ------------------------------------------------------ ,_ Ш » И ! 1 -

the mass of an object is accom­ I kilogram (kg) = 1 000 grams (g)

plished by a procedure called
weighing. An equal-arm balance 1 gram (g) = 1 000 m illigram s (m g)
is used to find the mass of an 1 m illigram (mg) = 1 000 m icrogram s (g g )
object.

EXAM PLE 1.2 C o n v e r s io n o f U n its in M a ss

P r o b l e m : Which number should replace the question mark in each of the following ?
a) 1 g = ?kg b) 1 mg = ? g с) 1 g g = ?g d) 1kg = ?g e) 5.3 g = ? m g f) 72 k g =
Solution : a) 0.001 b) 0.001 c) 0.000 001 d) 1000 e )5 3 0 0 0 72 000 000 ________

EXER C ISE 1.2 Change the following units o f mass as indicated in the Examrle 1.2
a) 5 kg = g b) 50 g = mg c) 10 kg =.... mg
d) 500 mg = g c) 700 gg = g 0 1600 g = kg
_______
1 .2 .3 VOLUM E
The space occupied by an object is called its volume T he soil*' ob­
je c t you alw ays e n co u n ter can b e reg u la r o r ir r - ^ a r , I f thpAolid is
reg u lar, th a t is, if it h as sides th a t can be m ea fe^ ’ its v o u m e can be
com puted from these m easured lengths.
T h e b a sic u n it o f v o lu m e in the m e tr -v’slcm ° 1 e c u bic m eter
(m 3). A n o th e r co m m o n ly u se d u n it is cer,tim e ter (cm 3)
(See F ig u re 1.2) fn r thp
T he traditional unit o f v o lu m e ^ terrTK _ r . surem ent o f liquids
in the m etric system is the liter (in v ert the unit! °r f efinec* as ond
cu b ic decim eter. (See T a b le 1.? of

Лите and Conversions

10 cm T A B L E 1.3 Units
-) = 1 milliliter (mL)
1 cubic centimeters = l liter (L)
1000 cubic (-liter = I cubic decim ctcr (d m 3

1L = 1000 cm 3 = 1000 mL r(m L ) = 1000 microliter (gL)

j er at 4*C = I kilogram (kg)
FIGURE 1 . 2 -r-. , 1 l i t t e r at 4 “C = l gram fpl
t r i p e rela- 1 m il l i 1 " —
tionship between cm and
liter.
6 Chapter 1

FIGURE 1 .3 Some common volume measuring devices found in a chemical laboratory.

. ■
E X A M P L E 1 .3 C o n v e r s io n o f U n its in V o lu m e
Problem : W hat nunbcr should replace the question mark in each of the following ?
a)27 mL *? pL b) 4.2 L =? mL c) 72 mL = ? L
d) 2.2 cm3 = ?L e) 57 cm3 H20 =?g 0 94 dm3 = ?mL
Solution : a) 27 000 b) 4200 c) 0.072 d) 0.0022 e) 57 0 94 000

EXERCISE 1 .3 Convert the following units of volume as indicated in the example 1.3
i) 10 mL=....cm3 b) 2L=.....cm3 c) 20 dm3=.... mL
d)_W4jL=....L e) 100 mL H20 = g 0 400 cm3 =....dm 3

e v o lu m e o f irreg u la r solid, if the solid d o esn 't d isso lv e in w ater, can be

b y m easu rin g the v o lu m e o f w a ter it displaces. G raduated cylinders are
да
s u sed for m easuring liquid volum es .

TEM PERATURE '

is a m eastfce o f hotness, o r the co n centration o f h eat en ergy per u n it m ass,
u rcd w ith a ’h e tem perature o f a body. T h e tem p eratu re o f a body is m eas-
used in d iffere, called th erm om eter. T h e re are sev eral tem p eratu re scales
the centigrade sentries. T h e m o st co m m on scales are C elsius scale (called
O n th e C elstd Fahrenheit scale.
F ah ren h eit scale, wife, w a te r freezes at 0°C and b o ils at 100°C. O n the
T h e SI u ses th e «v.es at 32°F and boils at 21 2 “F (F ig u re 1.4 ).
th e k e lv in (K )* . T h e rd ^ m p e ra tu re scale w h ic h has a degree u n it called
lated b y the e q u a tio n : 4p b etw een K elv in and C elsius d e g re es is re-

on is not used with Kelvi._ C + 273 J

 An Experim ental Science : Chemistry 7

-Boiling point
T he te m p e ra tu re s in th e se of water
scales a re re la te d as follows

°C _ °F - 32
( 1)
100 180

(2) К = ° С + 273 /

-Freezing point
of water

Comparison of the Fahrenheit, Celsius, and Kelvin temperature scales.

F IG U R E .1.4

EXA M PLE 1.4 C o n v e r tin g F r o m °C to °F

Problem : Mercury boils at 356.5 °C. W hat is the boiling temperature of mercury in °F?
Solution : We can use the equation :
°C °F - 32
S u b stitu tin g , w e g e t ,3F = (356.5) + 32 = <73.7 °F
100 180

E X A M P LE 1.5 C o n v e r tin g fr o m °F to °C
Problem : A student living in §anhurfa wanted to report the temperature as 99 'B o his frieid living in Is­
tanbul. What Celsius temperature should the student have reported to hisiriend ?
Solution : To convert to °C, we use the equation :

S u b stitu tin g , w e g e t °C - (99-32) - 372 С

180
The temperature should have been reported as 37.2 °C.

EXERCISE 1.4 (a) W hat Celsius temperature corresponds to a room lc9 c0 8 6 /v

* / 7 о 0^ у л
(b) What Fahrenheit temperature corresponds to -2—_ _ _ ’ 6 °F)

EXAMPLE 1.6 C onverting from °C to К

Problem : A clinical thermometer registers a patient’s tempera . 06 is thisIcmperature
in K ?
Solution : W e use the following equation to convert to К => К =3ю g ^
K= °C + 273 => K= 37.8 + 271
Jt> Ц
> K. W h at i:
1,1 “ ",c i" иш реш и гс
EXERCISE 1.5 A liquid is heated from 30' expressed
in °C ? (18°C )
8 Chapter 1

1.3 UNCERTAINTY IN SCIENCE

Y o u alw ay s m ak e m e asu rem en ts in y o u r ch em istry la b o rato ries and in
y o u r d aily life. In m ak in g m ea su re m en ts, calcu latin g resu lts, and rep o rtin g
them to other, you face certain problem s. O ne such problem is the u n certainty
involved in all m easurem ents.
U ncertainty has tw o m ain causes:
(1) the measuring limitations o f the tools used.
___________ (2) the skill and accuracy o f the observer.
20 1 22
| M | M1.) S uppose that three different student m easure the w idth o f th e ir chem istry
L illi
book w ith a ruler. T h e first one reports th at the b o o k is 21 cm w ide. T h e sec­
ond reports th a t the w id th o f the b o o k is 21.1 cm . T h e th ird o n e reports the
w idth o f the b o ok as 21.13cm . W hich o f these results is the m o st accurate ?
A s sh o w n in F ig u re 1.5, the sm allest d iv isio n s o n the ru ler are 0.1 cm
(1m m ) apart and the edge falls betw een tw o lines. It is obvious th at the w idth
is b etw een 21.1 cm and 21.2cm . T h e first tw o re ad in g s d o n 't tell all th a t is
k now n. So the m ost reliable reading is 21.13 cm b ecau se the edge o f the b o o k
^ -rur. is c lo se r to th e left line. A s a result, the w id th o f the book should b e reported
FIGURE 1.5 The -jreci-
sion of the ruler useaie- as 21.13 cm . In the above m easurem ent, the last d ig it is n o t certain b u t is esti-
termines the uncertaiity jn m ated . T h e re fo re, w e ca n e x p ect the m easu re m e n t to b e u n c erta in by about
the length measured. 0.01 cm .T h c re su lt can b e expressed as 21.13 ± 0.01 cm . T h e p re cisio n o f the
ru ler is ± 0.01 cm , th at is, the w idth o f the b o o k could be 21.12 cm o r 21.14
cm.
In g en eral, the m o st accurate statem en t co n v ey s w h at is k n o w n and no
m ore.

1.3.1 S IG N IF IC A N T F IG U R E S
T h e p re c isio n o f a m easu rem en t is in d icated by the n u m b e r o f figures
to record it. T he digits in a properly recorded m easurem ent are significant
T h ese figures include all those that are kno w n w ith certainty plus one
h ich is estim ated.
p i e : 12.4 g has three sig n ifican t figures.
12.47 g has four sig n ifican t figures.
Th\ 30.026 m has five sig n ifican t figures,
c a n t fig ur44 c a b le r u le s f o r d e te r m in in g th e n u m b e r o f sig n ifi-
(1) All h
7 .^digits are significant.
(2) Z eros P « 4 f ) l 7 , 1 0.070
7 .0 0 3 , .„en m n zer0 digits are significant.
(3) Zeros at the e, 10>070
sigm /icajtf to the fight o f the decimal point are

\o
 An Experim ental Science : Chemistry 9

(4) Zeros to the left o f the fir s t nonzero digit are not significant.
0.0002 has only o n e sig n ifican t figure
0.00204 has three sig n ifican t figures. •

EX A M P LE 1 . 7 D e te r m in in g th e N u m b e r o f S ig n ific a n t F ig u r e s
Problem : How many significant figures are there in each of the following numbers ?
a) 752.06 b) 6.0080 c) 3.4 d) 0.0039 e) 15 thousand 0 42000
Solution : a) 5 (all digits) b) 5 (all digits) c) 2 (all digits) d) 2 (only 3 and 9) c) 2 (1 and 5)
■f) Zeros at the end of a number and to the left of the decimal point may or may not be
significant.
To prevent this problem, 42 000 should be expressed in scientific notation
two sig. fig. three sig. fig. four sig. fig. five sig. fig.
4 .2 x 1 0 4 4 .2 0 x 1 0 4 4 .2 0 0 x 10 4 4 .2 0 0 0 x l0 4

EXERCISE 1.6 How many significant figures do the following measured quantities have ?
a) 36.40 mm b) 500 g c) 0.0006080 m d) 0.0008 kg c) 0.420 g Q 2.41x10s
a) 4 b) A t least I, at m o s t 3, c) 4 d) 1 e) 3 f) 3

1.3.1.1 SIGNIFICANT FIGURES IN MATHEMATICAL

OPERATIONS
(a) A D D IT IO N AN D S U B T R A C T IO N
F or addition or subtraction, the answer should have the same number o f decim al
places as the quantity having the least number o f decimal places.
3.247
41.66
+ 125.2 ^ (This number has only one decimal place)
170.1 ^ (Answer should be rounded to 1 decimal place)

T h e r u le s for r o u n d in g o f f th e n u m b e r s are:
(1) I f the digit to be discarded is greater than 5,the last retained digit is increased
by 1 |---------> digit to be discarded
37.457
1------------ sdigit to be retained
37.457= >37.46 (rounded to four significant figures)=>37.5 (to three significant
figures)
(2) I f the digit to be discarded is less than 5, the last retained digit is left unchanged

I--------------> digit to be discarded

132.534
*—--------— > digit to be retained

132.534=>132.53 (rounded to five significant figures)=> 132.5(to fo u r sig n ificant

figures)
10 Chapter 1

"(3) J f the digit to he discarded is equal to 5,

(a) the preceding digit is increased by 1 i f it is odd.
(b) the preceding digit is left unchanged i f it is even

94.235 —> digit to b e discarded 18.445 —> d ig it to b e discarded

1—> o dd n u m b er L ev en n u m b e r
94.24 —» (rounded to four 18.44 —» (rounded to four
_ significant figures) significant figures)

EXERCISE 1.7 Rewrite each of the following numbers in a way that includes four significant figures.
a) 12 14.3 b) 0.024045 с) l 800 000 d) ,5x 10' e) 158.35! f) 19.6050
a) 1214 b) 0.00241)4 c) l.SO O xltf d) 1.500x10 e) 15S.4 /) 19.60

EXERCISE 1.8 Perform the following calculations and round off the results to the correct number of
significant figures.
a) 5.03 + 0.00I + 12.9 = ? b) 82.27 - О.Ю75 = ? c) 36.7 + I I4.31 + 0.002 = ? d) 84.36 + 26.2 + 1.006 = ?
a) 17.9 h) S3.16 c) I S 1. 0 <1) 1 1 1. 6

(b) MULTIPLICATION A ND D I VI SI ON
F or m ultiplication and division, the num ber o f significant fig u res in the
answer should not be greater than the number o f significant figures in the least
p recise factor.
4 sig figures «— , ,------- > 3 sig figures

12.35 x2.94
= 44.279268
0.82
T [2 sig fi gures

The result, 44.279268, should be rounded to two significant figures. Then it is ex­
pressed as 44.

E X A M P L E 1.8 M u ltip lic a tio n a n d D iv isio n

Problem : Perform the following calculations, and round off the results to the correct number of significant
figures.
a) 625 x 5200 fe. 1600 x /"14400 . c) 82.6 x 0.004 d) 294 x 18.0
0.0015 x 0.040 225000 x 0.00016 ' 37.23 x 9.8 2.24 x 0.082

Solution :
a) 3.25x10 ь>
5.4x10
36
6.0x10°
•4 d) 5.29x10'
c) 0 3 ^ = 8x10
3.6x 10 0.18
 An Experim ental Science : Chem istry 11

EXERCISE 1.9 Perform the following calculations, retaining the correct number of significant figures
in each answer.

a)
2.78 x 1()4 ,,
= ? b)
1.235x1 ()’5 x 0.665 - 9

1 .8 x l0 6 3.0x10 2x 17.605

3 5 -14 10
с) П.бОхЮ x 3.5 x 10 _ ? ^ 9.54x10 x 3.0 x 10 _ ?

1.566xl04 x 2 .0 x 102 6.0x10 ’5

1.3.2 S C IE N T IF IC N O TA TIO N
V ery large and very sm all num bers are often encountered in scientific
studies. F o r exem ple, the m ass o f an in d iv id u al h y d ro g en atom is 0 .0 0 0 000
00 0 0 0 0 0 0 0 0 0 0 0 0 0 001 67 g; the n u m b e r o f m o lec u les in 2 g H 2 is 602
000 000 000 000 000 000 000
V ery la rg e and v ery sm all n u m b ers are e a sie r to, w o rk w ith them w hen
th e y are p u t in to e x p o n e n tia l form . S c ie n tific n o ta tio n (o r e x p o n e n tia l
n o ta tio n ) is u sed to sim p lify the h a n d lin g o f c u m b e rso m e valu es. W hen-
scien tific n o tatio n is em ployed, the valu e is ex p ressed in th e form , called the
exponential form
a x 10"
W h ere a, the decim al part, is a n u m b e r (1 < a < 10), and n, the e x p o ­
n en t o f 10, is a positive o r negative integer o r zero.
A n u m b er can be converted into the ex p o n en tial form b y m o v in g the
decim al point until there is only one nonzero digit to the left o f it.
'k F o r each place the decim al p o in t is m o v ed to the left, n is increased by 1.
'k F o r each place the decim al p o in t is m oved to the right, n is de­
creased by 1

F o r e x a m p le

1 X» & 3 = L829 x 106 2 = 4 -2x10' 6

6 5 4 3 2 1 place of decimal point 1 2 3 4 5 6

E X A M P L E 1.9 W riting N um bers in Scientific N otation

Problem : W rite the following numbers in scientific notation.
a) 346400 b) 0.00296 c) 0.00000008 d) 52 000 000 e) 0.082 0 22400
Solution : a) 3 .464xl05 b) 2.96x10 ‘3 c) 8.0x10 8 d) 5.2xl07 e) 8.2x10 ‘2 0 2.24xl04

EXER C ISE 1.10 W rite these numbers in scientific notation.

a) 45000 b) 27 500 000 c) 10 240 000 000 d) 0.00072 e) 0.00000206 0 0.000063
a) 4 .5 x 1 0 4 e) 2 . 0 6 x l 0 '6
12 Chapter 1
---------------------------
EXA M P LE 1 . 1 0 C o n v e r tin g fr o m S c ie n tific N o ta tio n to D e c im a l N o ta tio n
Problem : W rite the following numbers as decimals.
a) 2.94x10 -3 b) 16.2xl05 c) 4 .0 x l0 8 d) 6 .6 3 x 1 0 -1 e) 1.246x10'5 0 1.6x10'9

Solution : a) 0.00294 b) 1620000 c) 400 000 000 d) 0.663 e) 0.00001246 0 0.0000000016

EXER C ISE 1.11 Write the following numbers as decimals.

a )2 .8 x l0 4 b) З.ОхЮ10 c) 9.65xl04 d) 1 .6 0 2 2 x l0 19 c) 7 .6 x l0 '8 0 9.54x10 14

M athem atical operations involving exponential num bers are carried out in
the fo llo w in g w ays.

1. A d d itio n a n d S u b tr a c tio n
T h e ex ponential num bers m u st all be expressed w ith the sam e p ow er o f
10. T h e result, w hich has the sam e p o w er o f 10, is ob tain ed by a d d in g or
subtracting the decim al parts.
(6 .4 x l0 4) + (2.6xl03) = (6.4xl04) + (0.26x104) = 6.66xl04 = 6 .7 x l0 4
(6 .4 x l0 4 ) - (2.6x103) = (6.4x104 ) - (0.26x104) = 6.14xl04 = 6 .1xl04

2. M u ltip lic a tio n

T he decim al parts arc m ultiplied and the exponents o f 10 are added algebrai­
cally.
(2 .5 x l0 7) x (1.8xl04) = (2.5x1.8) x 10 7+4 = 4.5x10”
(3.6x10s) x (7.5x10 -8) = (3.6x7.5) x 105+(~8) = 2.7x10 ‘2

3 . D iv is io n
T he decim al parts are divided, and the exponent o f 10 in the denom inator
is subtracted from the exponent o f 10 in the num erator.

6.48X10'1! _ / 6.48
) x 10(_11) " (+4) =2.31x10 ” 5
A ^ О О (Л

4. T a k in g a root
(a) W h en a square root is taken, the n u m b er is w ritten in su ch a w ay that
the ex p o n en t o f 10 can be divided exactly by 2. T he an sw er is fo u n d by taking
the square root o f the decim al part and dividing the po w er o f 10 by 2.

V e .4 x l0 * = У б 4 х Ю " Ш= 8 .0 x 1 0 5

(b) W h en a cube ro o t is taken, the n u m b e r is w ritten in su ch a w ay that

the e x p o n en t o f 10 is exactly divided by 3. T h e an sw e r is ob tain ed by taking
the cube root o f the decim al part and dividing the po w er o f 10 by 3.

V 3 .5 6 x l( ) n = ^ 3 5 6 х 1 0 9 = 7 .0 9 x l()3
 An Experimental Science : Chemistry 19

EXAMPLE 1.21 D e te r m in in g th e S ta te s o f S u b sta n c e s, U s in g th e M e ltin g a n d B o il­

in g P o in ts
Problem : Melting and boiling points of some substances are given below. W hat are the physical phases of
these substances at room temperature ? ___________
Substance Melting point (“C ) Boiling Point ( °C )
A 0 100
В -20 1 10
lii 60 105 J
Solution : Substances are solid before melting point, they are gases after boiling point and they are liquid be­
tween melting and boiling points. Room temperature is 25 °C. At 25 "C, A is liquid, В is gas and С is solid.

d) E x p a n sio n
A s h eat is added to a m aterial, the k inetic energy o f the p articles in c rea s­
es. P articles m ove faste r and faster as th e ir en ergy increases. A s the particles
m o v e faster, they c o llid e w ith ea ch o th e r m o re v io len tly . T h e se c o llisio n s
push the particles farther apart. E ventually, the volum e o f the m aterial in creas­
es and the m aterial expands.
E ith e r liq u id s o r solids exp an d w h en heated: T he th erm al ex p a n sio n o f
e ith e r liq u id s o r solids depends on the su b stance, th a t is, th e ex p an sio n is a
c h a ra c te ristic pro p erty . T h e th erm al e x p an sio n s o f all g ases are the sam e,
therefore, it is not a characteristic property fo r gases.

E X A M P L E 1.22 R e c o g n iz in g th e C h a r a c t e r i s t i c P r o p e r t i e s
Problem : W hich one of the following is the characteristic property of the three states of matter:solids, liq­
uids and gases ?
I. Expansion with heat II. Boiling Point
III. Melting Point IV. Solubility
Solution : I. Expansion is the characteristic property of solids and liquids.
II. Boiling point is used for liquids only
III. M elting point is for solids.
IV. Solubility is used to identify all solids, liquids and gases.
Then the solubility is a characterictic property of the three states of mater.

EX A M PLE 1 . 2 3 U s in g th e C h a r a c t e r i s t i c P r o p e r t i e s to S e p a r a t e th e M ix tu r e
Problem : In order to get the solid salt from the mixture of iron dust, salt and sand, which sequence should
be followed ?
I.
Using magnet II. Filtration III. Dissolving in water IV. Evaporation
Solution : A n sw e r: I, III, II, IV
I. Iron dust is taken from the mixture by using a magnet.
III. Next the mixture is placed in water. Salt dissolves in water but sand settles down
II. Now the mixture is poured on a filter paper. The solution of salt-water passes
through the paper but sand remains on the paper.
IV. The filtrate is heated to evaporate all water. When the water is evaporated, the residue is only
solid salt.
20 Chapter 1

EXAM PLE 1 .2 4 D eterm ine the States of Substances U sing the C haracteristic P roper­
t ie s ________ _______________ _____________ __________ _
A ............. ~ л
—-^ S u b s ta n c e X Y Z
Pr()pcrt\L'~~'~-^_

Density + + +
Flexibility +
^Expansion + +
i i i i i i i J
Characteristic properties of X, Y and Z arc given in the table. What can be said about the physical phases of X,
Y and Z ?
Solution : A n sw e r: X Gas, Y Solid, Z Liquid.
Density is the characteristic properly of all solids, liquids and gases. Flexibility is for solids only. Expansion is
the characteristic property o f solids and liquids.

S O M E N EW TE R M S

B oiling is a process in which evaporation takes M eter is the standard unit of length in the metric
place throughout a liquid. system. It is also defined as one-millionth of the dis­
B oilin g point is the tem perature at which a tance from the equator to the North Pole.
substance change from a liquid to a gas. O bservation is something we actually see, hear
C h aracteristic property is a property that is or feel.
used to differentiate between subtances. S cien tific n otation is the representation of
Chem istry is the science that studies the compo­ cumbersome numbers in exponential form.
sition of subtances and the changes that they may un­ Significant figures are those digits in a m eas­
dergo. ured quantity that establish the precision which the
Density is the mass o f a unit volume of a sub­ quantity is known.
stance. Solubility is the maximum mass of a solid that
Energy is the ability to do work. will dissolve in 100 g (100 ml) of water to form a sat­
E x p erim en t is a controlled situation to test a urated solution.
natural law. T e m p e r a tu r e is the hotness or coldness o f a
F reezing point is the tem perature at which a body. It is related to the speed of the atoms or mole­
substance changes from a liquid to a solid. cules in the body.
M ass is the amount of matter in an object. T h erm o m eter is an instrum ent that measures
M atter is anything that has mass and occupies temperature.
space. V olum e is the am ount o f space occupied by an
M elting point is the tem perature at which a object.
substance changes from a solid to a liquid. W eigh t is the gravitational force that acts on a
body.
 An Experim ental Science : Chemistry 17

E X A M P L E 1 .15 C a lc u la tio n s U sin g th e D e n sity

Problem : The density of iron is 7.9 g/cm3. What is the mass of a cube o f iron that is 2.5 cm on an edge ?

Solution . Density (d) = 7.9 g/cm 1 d=— =s> m = dxV = 7.9 g/cm 3x l 6 cm 3 = 126 g
Volume (V) =2.5x2.5x2.5 = 16 cm J V

E X A M P L E 1.16 Calculating Density

Problem : W hen 29.40 g o f a metal is placed in a graduated cylinder containing 10 mL of water,the water
level rises to the 15 mL mark. W hat is the density of the metal ?

Solution : m = 29.40 g ] d = — = ^ 9-4° § = 5 .8 8 g/mL

V = 15 - 10 = 5 mL J V 5 mL

E X A M P LE 1.17 C a lc u la tin g D e n sity o f a M ix tu r e

Problem : If 4 L o f the gas X with a density of 0.6 g/L and the gas Y with a density of 1.2 g/L are mixed,
the density o f the mixture is found to be 0.8 g/L . How many liters of Y arc used ?
Solution : Density o f the mixtures can be calculated by the equation.
m x+ m y , , dxx V x+ dvx V v
dmix = TT-— ~ since m x= d xx V x and m y= d yx V y then cw = -
V x+ V y ' ’ ' V x+ V y

0.6 g/L x 4 L + 1.2 g/L x V 2.4 g + 1.2 g/L x V y

0.8 g/L = — = — -------- — ------- — => V y= 2 L
4 L + V y_________________ 4 L + V y__________*___________________________

E XA M P LE 1.18 C a lc u la tin g D e n s ity

Problem : Equal volumes of the liquids X and Y are mixed to obtain the mixture XY. The mass versus
volume graph of mixture XY and the liquid X is given aside.W hat is the
density o f the liquid Y ?
Solution : When equal volumes are taken, the density of the mixture is
calculated by the equation

From the graph : dmix = - ^ 3 = 1.2 g/cm 3 and dx = = 0.6 g/cm 3

5 cm 5 cm

3
<L+ dv , л 3_ 0.6 g/cm + d y A _^ A
{ ^ = ^ -1 ^ => 1.2 g/cm • " y.. =» dy= 2 .4 - 0 .6 = 1.8 g/cm

EXER C ISE 1.16 The density o f benzene at 25 *C is 0.88 g/mL. W hat volume does 352 g o f benzene
occupy ? 400 mL

EXERCISE 1.17 When 40 cm3 of dry sand which weighs 96g is placed in a graduated cylinder contain­
ing 20.00 mL of water, the water level rises to the 52.00 mL mark. What is the density of the sand particles ?
3 g/mL
18 Chapter 1

b) M e ltin g an d F r e e z in g P o in t
A s the te m p e ra tu re o f a solid is raised, its p artic les (atom s, m o lecu les,
io n s) u n d e rg o in c re a sin g ly v ig o ro u s v ib ra tio n . F in a lly a te m p e ra tu re is
reach ed at w h ic h th e so lid is co n v e rte d to a liq u id .^T h is p ro ce ss is called
m e ltin g . T h e rev erse o f this p ro cess is called fr ee zin g . T h e te m p e ra tu re at
w hich a pure solid m elts and the tem perature at w hich a pure liquid freezes are
identical. T h e tem perature at w hich eith er m eltin g o r freezing occurs is called
th e m e ltin g p o in t o f a solid o r th e fr e e z in g p o in t o f the liq u id . (T he
m ore d etailed k now ledge w ill be given about this subject in C hapter 5).
T h e freezin g and m elting points o f d ifferen t solids can be m easu red and
be used to differentiate betw een them , w hether they are identical o r different.

EXAMPLE 1.19 U s in g M e ltin g P o in t to D iffe r e n tia te B e tw e e n S o lid s

Problem : There is a mixture o f solids X,Y and Z. Which one of them can be separated from the mixture by
using their melting points ? *
Solution : W hile a substance is melting or boiling, the temperature remains constant. Since the mixture is
solid initially, melting point of X is70 eC, Y is 50 °C, and Z is 70 °C. Melting point is a characteristic property
of a substance. Y is different from X and Z. So the answer is Y.

c) B o ilin g P o in ts
W h en a liq u id is h eated, the tem p eratu re rises and th e rate o f e v a p o r a ­
tio n , ch a n g in g from liq u id to gas, in creases. E v e n tu a lly the liq u id b ecom es
so h o t that b ubbles o f gas are form ed w ithin the liquid. W hen this lakes place,
the liquid is said to be b o ilin g . T he te m p eratu re at w h ich the b o ilin g takes
place is called the b o ilin g p oin t o f the liquid. T he b o ilin g p o in t is a c h a ra c ­
teristic property that can be m easured experim entally.

E X A M P L E 1.20 D iffe r e n tia tin g th e F a c to r s th a t A ffe c t th e B o ilin g P o in t

Problem : Which one of the following doesn't affect the boiling point of a liquid ?
a) Nature of the liquid b) Pressure on the liquid
c) Purity of the liquid |F) Amount of the liquid
S o lu tio n : a) Boiling point is a characteristic property. Boiling points of different liquids arc different. So
the nature of the liquid affects the boiling points.
b) Boiling point is the temperature at which vapor pressure of liquid equals the pressure acting
on the liquid. When the outer pressure is reduced, the liquid boils easily and boiling point reduces.
c) Pure substances have definite boiling points. But the boiling points of impure substances
can change.
d) Characteristic properties don't depend on the amount of substances.
Then the answer is d
 An Experim ental Science : Chem istry 15

1.4 COMMON PROPERTIES OF MATTER

W h atev er you see around you is m atter. M atter is anything that has mass
and takes up space. As its nam e im plies, m atter can be recognized by its pro p ­
erties o f m ass and volu m e. V olum e and m ass are o ften used in terch an g eab ly
to m easure the quantity o f m atter.

(a ) V o lu m e : Volume, as defined before, is the space occupied by an

A t very h igh tem p e ra tu res
object. T w o p ieces o f m atte r can n o t occupy the sam e space at th e sam e tim e.
( > 5 0 0 0 ° C ) , m a tte r c o n ­
A ll m a tte r ex ists in o n e o f fo u r states; solid , liq u id , gas and p la sm a . E ach
s ists o f in d iv id u a l p o s i­
tiv e io n s and e le c tro n s . state can be identified by certain characteristics.
S u c h a sta te o f m a tte r is A solid is rigid, possesses a definite shape and has a v o lu m e very nearly
c a lle d p la s m a . MosL o f in d ep en d en t o f changes o f in tem perature and pressure. It is assum ed th at so l­
the u n iv erse is in form o f ids are p ractically in co m p ressib le and have defin ite vo lu m e. A liq u id flow s
p la s m a .
and thus takes the shape o f its container. L iq u id s, like, solids, are only slightly
co m p ressib le have d efinite volum es. A gas tak es b o th the shape and th e v o l­
um e o f th e con tain er in w hich it is placed. G ases are readily com pressible and
c ap ab le o f in fin ite expansion. L iquid and solid form s o f m a tte r h av e d efinite
v o lu m es. S cien tists h av e d ev elo p ed d iffe re n t m e th o d s and to o ls to m easu re
the v o lu m es o f e ith e r liquids o r solids.
G raduated cylinders are the tools fo r m easuring liquid volum es. T he v o l­
u m es o f re g u la r so lid s can be found b y m e asu rin g th e ir d im en sio n s and by
calculations. T he volum es o f irregular solids can be m easured by displacem ent
o f w ater.

(b) M ass: The am ount o f m atter in an object is called the m a ss o f that

object. So m ass is one o f the p ro p erties o f m atter, th a t iden tifies it. M ass can
be m easured w ith an equal-arm balance. T he equal arm balance gives us a w ay
o f c o m p a rin g m asses o f o b je ct o f any kind, reg ard less o f th e ir shape, form ,
color, o r w h at substance they are m ade of.

(c) * In ertia : U nless a n e t force acts on an o b ject, the o b jec t h as a te n ­

d ency to k eep its state o f rest o r uniform m otion in a straig h t line. T his p ro p ­
erty o f m a tte r is called "inertia".
M a ss, v o lu m e, and inertia, are the co m m o n pro p erties o f m atter. T h ese
p ro p erties are additive and d ep en d en t on the q u antity o f m a tte r being c o n sid ­
ered. M o re m atte r m ean s m ore m ass, m o re v o lum e, and m o re inertia. C o m ­
m o n properties cannot be used to identify substances.

1.5 CHARACTERISTIC PROPERTIES OF

MATTER

M easuring v o lu m e o f the substances and com paring th e ir m asses are n o t

enough to distinguish betw een them . T w o objects can be m ade o f different
* For detailed description of inertia , refer to physics’books fo r lycee'l.
 16 Chapter 1

m aterials b u t can have the sam e m ass. O n the o ther hand, tw o objects can have
d ifferen t m asses and be m ade o f the sam e m aterials. M ass is a pro p erty o f an
o b ject b u t it is n o t a property o f the substance o f w h ich the ob ject is m ade.
If w e w an t to find o u t w hether tw o objects can have different m asses and
be m ad e o f th e sam e substance o r o f d ifferen t su bstances, w e h av e to lo o k fo r
p ro p erties th a t do n o t depend on the am o u n t o f th e substan ce o r o n the shape
o f th e sam ple. The properties that differentiate betw een two substances are
called " c h a r a c teristic p ro p erties" . D ensity, m e ltin g p o in t, b o ilin g p oint,
solubility and expansion are som e exam ples to the characteristic properties.
a ) D e n s ity
The mass / volume ratio o f a given substance is called its d en sity. (F ig ­
u re 1.6) D ensity is usually defined as th e m a ss o f a u n it v o lu m e o f a
Volume (cm3) V su b s ta n c e . A su b stan ce m ay b e id en tified b y its d en sity . T h e d e n sity o f a
pure substance rem ains constant fo r a specific tem p eratu re. T h e density, does
FIGURE 1.6 The mass
of a substance is directly n o t d ep en d o n the am o u n t o f the su b stance. T h e d en sity o f a p u re su b stan ce
proportional to its volume. can change w ith changes in tem perature. T h e density decreases slightly as the
The ratio of mass to vol­ tem perature rises. The definition of density can be expressed mathematically as
ume is called density.
This ratio is equal to the'
slope of the line in m - V D e n s ity = a ss or in symbols d = —
V o lu m e V
graphs.
S lo p e = t a n a = m
T h e u n it o f d en sity is gram p e r cu bic ce n tim e te r (g /c m 3) o r gram s p e r
V (cm )
m illiliter (g/m L ), depending on w hether the substance is a solid o r a liquid.
In m ass v ersus v o lu m e graphs, the slope o f th e lin e gives the density o f
th e su b stan ce. S ee F ig. 1.6.
T A B L E 1.4 D ensities o f Som e C ommon Substances
r ............ .........
SOLIDS LIQUIDS ^
Substance Density in g/mL. Substance D en sity in g/m L .

alum inum 2.7 benzene 0 .8 8

copper 8.9 e th e r 0 .7 1
c o rk 0 .2 0 e th y l a lc o h o l 0 .7 9
g o ld 1 9 .3 g a s o lin e 0 .7 0
quartz 2 .6 g ly c e rin e 1 .2 6
ice 0 .92 m ercury 1 3 .6
iro n 7.9 sulfuric acid 1 .8 4
m ag n e siu m 1.7 w ater 1.00
lead 1 1 .3
p in e 0 .6
G A SES
p la tin u m 2 1 .4
s ilv e r 1 0 .5
sodium 0.97 h y d ro g e n 0 .0 0 0 0 9
tab le sa lt 2 .2 oxygen 0 .0 0 1 4 3
tin 7.3 n itro g e n 0 .0 0 1 2 5
uranium 1 8 .7 carb o n d io x id e 0 .0 0 1 9 9
z in c 7.1 air 0 .0 0 1 2 9
V .J
 An Experim ental Science : Chem istry 13

5 . R a is in g to a p o w er
W h en a n u m b er is squared, the decim al p art is squared and the ex p o n en t
o f 10 is m ultiplied by 2 .
(9 .4 5 x 1 0 6)2 = (9.45)2 x 102(+6) = 8 9 .3 x l0 12 = 8 .9 3 x l0 13
W h en a n u m b e r is cubed, the d e cim a l p art is cubed and the e x p o n en t o f
10 is m ultiplied by 3.
(3.4x1 O'3)3 = (3.4) 3x l 0 3(-3) = 39x10"9 = 3 .9 x 1 0 ' 8
In general nm m mxn
(a x 10 ) = a x 10

E X A M P LE 1 . 1 1 M a th e m a tic a l O p e r a tio n s B a sed on E x p o n e n tia ls

Problem : Perform the following calculations.
(2.40x10 -4 +6.26x10 -3) (6.4x106 - 4.0x105)
a) ------------------------------------------ =? b) =?
(4.60x 105x 1, 8 x 106) (1.76x10-3x 2 .2 4 x l0 5)

(2.40x10 -4 +62.6x10 -4) 65.0x10 ' 4

Solution a) = — =7.8x10-15
(4 .6 0 x l.8 )x l0 5+6 8.3xlOn

(6.4x10 6 - 0.40x106) б.ОхЮ 6

b) = — = 1.5xl0 4
f 1.76x2.24; 10 3,5 3.94x102

EXERCISE 1.12 Express the answer to following operation in scientific notation.

45.10x2.451x10 -5x4.431xlO 3

6 .0 2 2 x 1 0 ' 23x 2 . 0 5 1 x 10 25 3.96 6x10 - 9

E X E M P LE 1.12 M u ltip lic a tio n a n d D iv isio n o f E x p o n e n tia l N u m b e r s

Problem : Perform the following calculations, expressing the answers in scientific notation.
, lx lQ 6 b) 4.5x10^ . 1.45x10^
2 4 -12
1x10 5x10 5.0x10

d) 2 x l0 4 x 3 x l0 4 e) 3 .1 x l0 '3 x 2 .0 x l0 ‘5 0 4 .3 x l0 ‘5 x l.OxlO2

Solutions :
14 Chapter 1 -------------------

с) 1-45x10 _ = 0'.29 x 104 = '2 .9 x' 1()3 d) 2 x l0 4 x 3 x l0 4 = 6 x l()8

-12
5.0x10

c ) 5 .1 x 1 0 3 X 2 . 0 x 1 0 5 = 6 .2 X 1 0 s f) 4 .3 x 1 0 ° ' x l.O x lO 2 = 4 . 3 x l O '3

EXERCISE 1.13 Perform the following exercises. Expressing the answer in scientific notation.
a>>% b ) 2xl(l c ) i- ! ? 10- d )-? x l°fx w :
IxlO 5 x 10 3 7x l()4 4x10."

C) 2. 5x 10 :\\4x l ()4 f) 0.6.x I()!x0.05x 10 s

EXAMPLE 1.13 T a k in g S q u a r e and C ube Root

Problem: а) Так,e the square root of 0.625x10 '3 _3 4
b) Take ih rt cube root of the mathematical operation 0.2x10 xO,15x10 x9xl0
1x102
Solution: а) 1 6 2 5 x 1 0 '' = V 625x10* = 25 x 1o'" = 2.5x 10 '
/ _ / 0,27x10 _ Vo. 27xof" = M
0.2x10 x0.15x10x9x10
127x10 -6= 3x 1 0 -2
1x102 V 1x10
EXERCISE 1.14 Take the square and cube, root of the following ow i о ■.
а) 1 / 2.0x l(t \3.2x 10 b) \2.0.x It) "\ ;

a)2.5x10* l>)1.9x10'
EXAMPLE 1.14 R a is in g to a Rower
Problem: Carry out the following operation. 3 -4

a) (2.5x Ю3) 2 b) (2 x l0 2+ 4 x l0 3) 2 ) ( —^ ) c
1x10 “

Solution: a) (2.5x 103)2 = 6.25x106 b) <2x 102+40x 102)2 = (42x 102)2 = 1764xI04 = 1.764xl07
^ 3x10 j = (3x1 O'2) = 27x10 ° = 2.7x10 °
-4 3
. c)
IxlO '
EXERCISE 1.15 P e rfo rm th e fo llo w in g c a lc u la tio n s a s in d ic a te d in e x a m p le 1.Ы
a) (3xl0;!r bi (2x10V с) ( :4л1П< ' ч |° )
2x10'
 An Experim ental Science : Chemistry 21

/ R E V IE W Q U E S T IO N S
1-1 ...........................may be m easured in gram s j . jo w h y isn't there any negative value in Kel-
per cubic centimeter. vin scale ?
1.2 Anything that has mass and takes up space is 1.11 How would you change a given num ber of
...................................................... meters to centimeters ?
1.3 The state of m atter on the surface o f the sun , f
1.12 How would you change a given number ot
is
cubic centimeters to liters ?
1.4 A substance which has a definite volume but
. , , c .. . . . ,, 1.13 W hat physical properties could you use to
tak es the shap e o f its c o n ta in e r is in the F 3 v 1 3
tell the difference between the following pairs of mat-
.................................state.
ter.
1.5 W hat does it mean for a substance to be
denser than another ? a) coal-snow b) vinegar-water
1.6 Vinegar and salad oil arc two liquids which c) lead-aluminum d) salt-sugar
do not mix. W hich liquids floats on top of the other? j dissolves in w ater but naphthalene
3 3
Why ? doil = 0.92 g/cm dvinegar =1.01 g/cm doesn't dissolve in water. How can you separate them
1.7 W hy does oil float on water ? from a mixture of salt and naphthalene ?
1.8 W hat is evaporation ? 115 Some cork and lead particles are mixed.How
1.9 W hat happens when water boils ? can you separate them ?

" REVIEW PROBLEMS

1.16 Perform the following unit conversions 1-20 Express each of these numbers as a number
a) 0.26 dam = ? cm b) 0.72 mm =? hm between 1 and 10 multiplied by 10 raised to a power.
c) 1.8 m = ? pm d) 700 mL = ? L a) 21250 b) 190000 c) 0.00001280
e) 0.75 dm 3 = ? pL f) 36 m 3 = ? L
g) 240 mg = ? kg h) 1.8 p g = ? mg 121 СаггУ out the following operations and ex-
i! 25 - i к kl 38°C - ? °F ! press each answer in scientific notation.
1 2 7°c"= '9 К m l 392 °F~= ? К a) 2 .3 x l0 4+ 4 .6 x l0 4 b) 2 .3 x l0 4+ 5 .3 x l0 5
’ c) 2 .5 x l0 4x 4 x l 0 '3 d) 2.5x10 ц / 0.5x 10 '2

1.17 How many significant figures are there in

each of these numbers ? Express each of the follow ing numbers as
a) 154 b)0.06410 c) 1042 decimals.
d) 2420 e) 2.2 3 x l0 5 f) 5 thousand ^ 8'5 x l° 1-6415x10 c) 8 .010 x 10

„ . ._ 1.23 Change the following to powers of ten

10 ” a> 448x104 - 4 -48хю7 ь> 2 -35xi° 4 - xi05

a) 4.568 b) 5.144 c) 2.505 c) 324.5x10’ -....x lO 11 d) 0.045x10 4.5x101
d) 35.45 e) 0.001064 f) 1481
1.24 The boiling point of alcohol is 78 °C and
1.19 Express the answers to these problems us- the freezing point i s -115 C. Suppose Celcius had
ing the correct number of significant figures. selected these temperatures as the fixed points o f his
s i m e п л о т id cc п и т е thermometer, and called them 100 °C and 0 °C, would
a) 1.425+0.0841+14.55+0.0015 = . c , , . , ’ ,„
' the size of a degree have been increased or decreased ?
bl 17.1 x 3.14 x 331 =
Increased
117 R9 j- n 913 94 0 - 1-25 A block o f metal has a mass of 88.75 g and
” a volume of 12.5 cm3. W hat metal might it be?
d) 0.01830 + 1.1940 - 1.001 _ ^ 7.1 g / c m ^ , z i n c
0.27
22 Chapter 1

1.26 A mass of 600 g of sugar is dissolved in 600 1.30

mL of water yielding 960 mL of sugar solution, a) r
Substance mp CC) bp(°C ) Л
Calculate the density of the solution in g/mL. b) How
many milliliters o f this solution contain 100 sugar ? Benzene 5.5 80.1
1.25 g/mL, 160 mL. Chloroform -6 3 .5 61.3
1.27 100 mL of water arc required to fill a bottle. Chlorine - 101 - 34.1
125 g of another liquid will fill the same bottle. Com­ Mercury -3 9 357
pute the density of other liquid. 1.25 g/mL
Sulfur dioxide -7 3 - 10

ОС
ОС
o\
1.28 Calculate the mass of each of the following: ^S odium 98
a) a sphere of aluminum o f radius 5.00 cm
b) a cube of magnesium of edge length 0.025 mm. The melting points and boiling points of some pure
c) 4.00 L o f oxygen gas (doxygen = 0.00143 g/mL) substances are given in the above table.
a) Indicate the physical state of each of them at room
d) LOO m 3 of air (dair = 0.00129 g/mL)
temperature, 25°C.
*1.29 When equal volumes of liquids A and В are b) Which one (s) of these substances is liquid at
mixed, a solution with a density of 1.2 g/mL is ob­ 100°C ?
tained. When equal masses of these liquids are mixed, c) For which substance (s) expansion is not a charac-
the density of the mixture is found to be 0.9 g/mL. terictic property ?
Find the density of each liquid. d) At room temperature for which substances can flex­
ibility be used as a distinguishing property ?

SELF TE S T
1. Which one of the following unit conversions is 4. How can the answer be expressed using the cor­
WRONG ? rect number of significant figures ?
A) 2.45 g = 2.45 x 103 mg B) 2 pm = 2 x 10'6 m 656.10-0.475=?
C) 284 mL = 0.284 L D) 37°C = 310 К A) 655.625 B) 655.63 C) 655.62
E) 2.5 dm 3 = 250 mL D) 655.6 E) 656

2. W hich one o f the follow ing statem ents is 5. Which of these conversions are CORRECT ?
W RONG? • I. 0.0021 = 2.1 x 10'3 II. 1.82x1 O'4 = 0.0182
A) The number, 123 .contains 3 significant figures III. 0.035 x 108 = 3.5 x106 IV. 2.61 x 104 = 26100
B) The number,0.01230,contains 4 significant fig­
A) I, II, III В) I, И, IV С) I, III, IV
ures
D) I, И, III, IV E) I, III
C) The number, 1.23xl0"2, contains 3 significant
figures
6 . W hat is the result of the given mathem atical
D) The number, 1.230x1 O'2, contains 3 significant
operation ? -4 -з
figures 1 1.6x10 +0.04x10 = ?
E) The number, 12300 contains at least 3, at most
5 significant figures 4 x l0 ~2
A) 5 x 1 0 '3 B) 5x10 "7 C)4 .1 x 1 0 '5
D) 4 .1 x 1 0 '9 E) 5x10' 1
3. Some numbers are rounded off to two signifi­
cant figures. Which one of them is W RONG ?
A) 1.350 -> 1.4 B)1.657 -> 1.7 Q 1 8 . 4 5 18 7. What is the square root of 0.064x10 '5 ?
D) 1.973 x 102 -> 2 x 102 E)0.0786 -» 0.079 A) 8 x l0 "3 B) 8.0x10 "4 C) 0.8x10 "4
D) 8 x l0 ' 8 E) 0.8x10 -6
 A n Experimental Science : Chemistry 23

8 . The following procedure was carried out to find should be used ?

the density o f a liquid. A graduated cylinder was A) Expansion B) Mass C) Odor
weighed empty and then filled with the liquid X until D) Solubility E) Color
its 40.0 mL mark. If the masses of empty cylinder and
filled cylinder are 224.60 g and 256.20 g, which is the 15. Which one of the following properties depends
density of the liquid X ? (The answer m ust be ex­ on the amount of matter ? . “
pressed in correct number of significant figures.) A) Melting point B) Boiling point (^C) Volume
A) 0.8 g/m L B) 0.79 g/mL C) 0.790 g/mL D) Density E) Solubility
D) 0.95 mL E) 1.12 g/mL
16. Melting and boiling points of substances are
9. One liter of water at 27°C is heated to 400°K. given_
What is the change in the temperature of water? f substance m.p. (°C) b.p. (° c )]
A) 327°C В) 273°C C) 600°C D) 127°C E) 100°C A - 160 - 10
В 15 130
10. How many grams of liquid gallium fills a 25 t С 60 210 J
mL vessel ? Density o f gallium is 5.88 g/mL.
© 4 .2 5 B) 0.2 C) 147 D) 250 E) 5.88 Which one is correct for the physical phases of
substances at 25°C.
11. A regular block of gold with dimensions 2.0 A) A solid, В liquid, С gas
стхЗ.О cm .\5.0 cm weighs 570 g. W hat is the density B) A gas, В liquid, С solid
of the gold ? C) A and В gas, С solid
A) 280 B) 190 C) 114 D) 19 E) 9.5 D) All gases
E) All solids
12. A liquid was mixed with water to obtain a so­
lution with a density of 1.1 g/mL. W hat can be said 17. Which one isn't a characteristic properly of liq­
for the density of the liquid ? d([i2o) = 1 g/mL uids ? - ■
A) I c 'd < 1 .1 B) 0.9 < d < 1 C) 1.1 < d A ) Flexibility B) Density C) Boiling point
D) d = 1 E) W e can't say anything. D) Solubility E) Expansion

When the equal vol­

13. 18. Which one of the characteristics below doesn't
umes o f liquids A
m (g) and В are mixed, a have a function to differentiate copper and zinc ?
hom ogeneous m ix­ A) Density B) Volume C) Expansion
ture (A+B) is ob­ D) Melling point E) Flexibility
tained. The graph
given aside show s 19. Which one can not be the characteristic proper­
the relationship bc- ty of a solid ?
1 0 .y, (mL) tw een the mass of A) Density CE) Mass C) Solubility
the mixture,(A+B), and its volume. Which ture the den­ D) Flexibility E) Melling point
sities in g/mL of the liquids A and B?
20. Which ones of the follow ing'can not be the
A) 1.0-1.5 В) 1.2-1.5 C) 1.0-2 D) 1.0-2.5 E) 1.0-3.0 characteristic property of a gas ?
I. Density, II. Expansion, III. Volume,
14. In order to separate a mixture of sand and table IV. Solubility
salt into its com ponents, which property o f water A) I,II В) I, III C ) II,IV D) I, IV Щ) II, III
 CHAPTER

A Scientific ModelrAtomic Theory

The objectives of this chapter are to enable the student to :

1.Classify matter according to its composition as elements,
com pounds, homogeneous or heterogeneous mixtures.
2 .Recognize the atom ic symbols of more common ele­
m ents.
3.Write the formulas of chemical compounds.
4 .Distinguish between the empirical and molecular form u­
las of a compound.
5.Write the names and symbols of common cations and an­
ions.
6.Write the names and formulas of binary ionic and binary
covalent compounds.
7 . Name s o m e of the more common polyatomic ions, and
write names and formulas of compounds containing these ions.
8 .Recognize the relative atomic and molecular weights.
9.Discuss the mole concept as applied to atoms and mole­
c u le s .
10.Determine the number of atoms in a given sample of an
element or number of the molecules or formula units in a given
mass of a compound.
11.Determine the percent composition of a compound.
1 2.Determ ine the em pirical and m olecular form ulas of a
com pound given its percent com position and its m olecular
weight.
 A Scientific M o d e l: Atomic Theory 27

2.1 CLASSIFICATION OF MATTER

A s d efined before, m atter is anything th a t has m ass and occupies space.
T h e m a tte r a t v e ry h ig h
M a tte r e x ists in fo u r states, so lid , liq u id , g as, an d p la sm a , d e p e n d in g o n
tem p e ra tu res g re a te r th en
the tem p eratu re and pressure.
5000°C th e c o llis io n s
b e tw e e n p a rtic le s are so T h e experim ental studies show ed that all m atter, w h eth er it is in the form
v io le n t th a t m a tte r d e ­ o f so lid o r gas, co nsists o f very sm all p article s c alled a to m s o r m o lecu les.
c o m p o s e s in to its s u b a ­ A n a to m is the sm a lle st p a rtic le o f m a tte r th a t ch a ra cterizes an elem ent. A
to m ic p a rtic le s; e le ctro n s
m o lecu le is a com bination o f a tom s th a t can ex ist as an in d ivid u a l u n it h a v ­
and p ro to n s. S u ch a sta te
ing a se t o f p roperties.
o f m a tte r is c a lle d p la s ­
m a. M o st o f the u n iv erse A ll m a tter w hich occurs in o u r en v iro n m en t can b e classified into one o f
c o n sists o f p lasm a . sev eral categ ories show n in F igure 2.1

C h em ic al Same properties T w o or m ore phases,

each w ith its own
re a c tio n s th ro ug ho u t
set o f p rop erties

FIGURE 2.1 Classification of matter

2.1.1 PURE SU B S TA N C E S
The su b stances w hich have characteristic p ro p e rtie s (as given in section
1.5) a re k n o w n as p u r e su b sta n c e s. P u re su b sta n c e s can b e c la ssifie d as
o n e o f tw o ty p es, c o m p o u n d s o r ele m e n ts.
E lem ents are the basic units o f m atter that cannot be decom posed by o rd i­
n ary ch em ical m eth o d s into sim p ler substances. A t the p rese n t tim e, 106 e le ­
m e n ts are k n o w n . A b o u t 9 0 o f th e se e lem en ts h av e b e e n founcT.in n a tu ra l
sources; the rest o f the elem ents are artificial. Som e exam ples o f elem ents are;
o x y g en , carb on, m ercury, gold, iron, e tc ...
C o m p o u n d s are su b sta n ces th a t are co m p o sed o f tw o o r m o re elem ents
in f ix e d p ro p o rtio n s. C o m pounds h av e p ro p e rtie s th a t are d iffere n t from the
p ro p e rtie s o f ele m en ts o f w h ic h th ey are co m p o sed . C o m p o u n d s c a n b e d e ­
c o m p o sed in to sim p ler sub stan ces b y ch em ical m eth o d s. S om e ex am p les to
co m p o u n d s are w ater, sugar, salt and carbon dioxide.
28 Chapter 2

EXA M P LE 2.1 Identifying an Element

Problem: Which one of the following is not related to an element ? An elem ent...
a) consists o f only one kind o f atoms.
b) has its own characteristic properties o f melting point, boiling point, density, etc...
c) can be separated into simpler substances by ordinary chemical methods.
d) is a pure substance.
Solution: Answer : C. Because an element is the simplest form of matter and cannot be decomposed into
simpler substances by any chemical method.

EXA M PLE 2.2 Identifying a Compound

Problem : Which one of the following experiments must be performed to identify water as a compound ?
I. W ater is evaporated at a constant pressure.
II. Water vapor is condensed and then frozen.
III. Water is electrolyzed into hydrogen and oxygen.
Solution : Answer II and III.
I. There is no certain vaporization point for liquids.
II. M elting point (or freezing point) and boiling point (or condensing point) are characteristic properties o f pure
substances. Therefore water could be an element or a compound.
III. The decomposition o f water into hydrogen and oxygen shows that it is a compound. Because a compound
consists of two or more elements.

2.1 .2 M IX T U R E S
M o st m a tte r in o u r ev ery d ay lives is a m ix tu re o f substances. T h e food
w e eat, th e w a te r w e drink, the air w e b reathe and the "pure" soap w e use are
all m ix tu res. M ix tu res co n sist o f tw o o r m o re p u r e su b stances. U nlike p u re
su b stan ces, they have v ariab le co m p o sitio n . T h e p ro p e rtie s o f a m ix tu re d e ­
p en d u p o n th e co m p o sitio n o f the m ix tu re and th e p ro p erties o f the pure su b ­
stances th a t form the m ixture. T h ere are tw o types o f m ixtures.
(a) H o m o g e n e o u s m ix tu r e :
A h o m o g eneous m ix tu re has the sam e p ro p erties (eg. density and co m ­
p o sitio n ) th ro u ghout. E x am p les are th o ro u g h ly stirred m ix tu res o f su g ar and
w a te r o r salt and w ater. W e call a ho m o g en eo u s m ix tu re a solu tion .
(b) H e te r o g e n e o u s m ix tu r e :
A h etero g eneous m ixture is n o t un ifo rm th ro u g h o u t b u t consists o f parts
o r p h ases th at d iffer in properties. A m ixture o f g aso lin e and w ater is an ex am ­
ple o f a tw o -p h ase m ixture in w hich the gaso lin e floats on the w a ter as a se p ­
arate layer.
M ix tu res can be fo u n d in one o f fo u r states o f m atter. T h e m ix tu re o f
p o w d e re d iro n and p o w d ered su lfu r is an ex am p le o f h e te ro g e n e o u s solid
m ixture. In th is m ixture the individual ingredients still retain th eir characteris-
 A Scientific M o d e l: Atomic Theory 29

tic properties. Iron can be separated from the m ixture using a m agnet, b u t su l­
fu r c a n n o t b e separated from the m ix tu re u sin g a m ag n et, w h ereas su lfu r can
b e sep arated by d issolving it in the so lv en t c arb o n disulfide. T h e resulting so ­
lu tio n o f su lfu r d isso lv e d in c arb o n disu lfid e is a h o m o g e n eo u s m ix tu re. B y
sh ak in g v ig o ro u sly you ca n prepare a m ixture o f olive oil and w a te r in w h ich
olive oil p articles are suspended th roughout the m ixture. T h e colloidal d isp er­
sio n o f a liquid in an o th er liquid is called an em u lsio n . C o n sid e r the m ixture
o f w ater and clay o r sand. Such a m ixture is a m ulti-phase m ix tu re k n o w n as a
su s p e n s io n . A su sp en sio n is a m ix tu re in w h ic h the p artic les o f o n e ( o r
m o re) o f th e su b stances are relativ ely large. U nless a su sp en sio n is stirred o r
shaken, th e large p articles w ill so o n er o r la ter settle out. S u sp en sio n s o f so l­
ids in liquids can be separated by sim ple filtration.
T h e m ix tu re o f tw o o r m o re gases alw ays fo rm s a h o m o g en eo u s m ix ­
ture. T h e resulting m ixture is a solution.

EXA M PLE 2.3 S e p a r a tio n o f M ix tu r e

Problem: Suggest some methods to separate the following mixtures.
(a) Blood (b) Petroleum (c) Mixture of water and clay
(d) Mixture of sodium bicarbonate and ammonium chloride (e) Mixture of powdered iron and powdered sulfur
Solution:
(a) Blood is a suspension. Its red and white cells can be easily separated from the plasma by a centrifuge.
(b) Petroleum is a mixture consisting of fractions of gasoline, kerosene, jet fuel, diesel fuel, etc... Bach of frac­
tion has different boiling point, therefore the separation of petroleum is based on the difference in boiling points
of each fraction. This method is said to be fractional distillation.
(c) As many suspensions, the mixture of water and clay can be separated into its components by filtration.
(d) Sodium bicarbonate is quite soluble in hot water but moderately soluble in cold water. On the other hand,
ammonium chloride is quite soluble in cold water and extremely soluble in hot water. These facts suggest that
this mixture can be separated by fractional crystallization (recrystallization).
(e) This mixture can be separated into its components by using a magnet or by dissolving sulfur in carbon
disulfide.

EXA M PLE 2.4 S e p a r a tio n o f M ix tu r e

Problem : Salt is a solid which dissolves in water but starch doesn't. How can you separate the mixture of
salt and starch ?
Solution : The mixture is placed in water. Salt dissolves and becomes a part of solution. Starch remains as
solid. The solid may be separated from the liquid by filtration. The solid remains on the filler paper. The solution
which passes through the filter paper contains salt and water. If the solution is heated to evaporate all the water,
solid salt remains behind.

EXERCISE 2.1 In three beakers there arc alcohol, oil, and gasoline respectively. Which experiment is
most useful to separate them ?
30 Chapter 2

2.2 SYMBOLS AND FORMULAS

T A B L E 2.1 P e r c e n ta g e
As defined earlier, an clem ent is one o f a group o f fundam ental
a b u n d a n c e s o f E le m e n ts
su b sta n c e s th a t c a n n o t b e b ro k e n d o w n in to sim p le r su b sta n c es. A t
ШДОВ 4V.2 | p re se n t 106 d ifferen t elem en ts are know n. A b o u t 90 o f th ese elem en ts
| silicon 25.7 c a n be e x tra c te d fro m n a tu ra l so u rces; th e re st h a v e b e e n c re ated
aluminum 7.5 th ro u g h n u c le a r p ro c e sse s. T h e 10 m o st a b u n d a n t e le m e n ts in the
:;§Щ iron 4.7 e a rth 's cru st, b o d ie s o f w a te r and atm o sp h e re are listed in T a b le 2.1.
jljllll calcium 3.4
O n th e o th e r h an d , the m o st a b u n d a n t e le m e n t in the u n iv e rse as a
j sodium 2.6
w h o le is h y d rogen, w h ich is th o u g h t to co n stitu te ab o u t 75% o f the to ­
iijlj potassium 2.4
tal m ass o f the universe.
Щ magnesium 1.9
A cco rd in g to th e ir physical and ch em ical p ro perties, elem ents can
hydrogen 0.9
b e c la ssifie d into th ree groups; m e ta ls, n o n m e ta ls, and m e ta llo id s.
i] titanium 0.6
A b o u t 80% o f th e k n o w n e le m e n ts are m e ta ls.A co m p a riso n o f the
til all others 1.1
characteristic properties o f m etals and nonm etals are given in T able 2.2.

TABLE 2.2 C h a ra cteristic p roperties o f m eta llic a n d n o n m e ta llic elem en ts

л M e ta llic e le m e n ts N o n m e ta llic e le m e n ts л

1- Lustrous, shiny when cut freshly 1- Nonlustrous (dull), various colors.

2- Solid at room temperature (with the ex­ 2- Solid, liquid and gas at room temperature.
ception of mercury)
3- Good conductors o f heat and electricity 3- Very poor conductors o f heat and electrici­
ty. (except carbon in graphite)
4- Malleable (can be hammered fiat) and 4- Solids arc usually brittle, may be soft or
ductile (can be drawn in wire) hard.
5- Tend to give only electrons to produce 5- Tend to gain or loose electrons to produce
^ cations (positively charged ions) cations and anions (negatively charged ions)

T h ere is a v ery lim ited n u m b e r o f elem ents that have the properties o f b o th m etals and nonm ctals. T hese
are called m e ta llo id s. S ee F ig .2 .2 .
"1 n o n m c ta ls m e t a ll o id s m e t a ls

Li Be В С o2 Ne
F*

No. A /y At Si P+ S,s C‘z A t

К Co. Sc Ti V Cr Mn Fe Co N i Си Zn Ga. G-e As Se B r2 Kr

Rb Sr Y Zr N b■ Mo Tc Ru Rh Pd a 9 Cd In Sn Sb Те I2 Xe

La -
Cs Ba H f Та W Re Os Jr Pt Au H9 Tl Pb Bi Po A t Rn
Lu
Ac - 1 i
Fr R a.
Lw
_ .j

La. Ce Pr Nd Pm Sm Ru Gd Tb Dy Ho Er Tm Yb Lu

Ac Th Pa U Nj> Pu Am Cm Bk Cf Es Fm M d Lw

FIGURE 2.2. Classification of elements as metals, nonmetals, and metalloids.

 A Scientific M o d e l: Atomic Theory 31

2.2.1 S Y M B O LS
A ll o f the elem ents have nam es but ea ch clem en t has b een also assigned
its o w n u n iq u e sy m bols, w h ich w e w ill find usefu l fo r w ritin g c h em ical fo r­
m u las and chem ical equations. T h e nam es o f the elem ents ch ange a little from
one lan g u ag e to another, b u t sym bols do not.
T h e sym bols are form ed from one o r tw o letters o f the nam es o f the clc-
m cn ts.T h e first letter, regardless o f the origin o f the sym bol, is alw ays cap ita l­
ized and the second letter is alw ays w ritten in lo w er case.
T h e sy m b o ls m a y b e d iv id e d in to fo u r m a in g r o u p s.
1. A few sym bols arc derived from the old L atin ( o r o th e r foreign except
E ng lish ) nam e. T he elem ents w ith sym bols derived from the old L atin o r F o r­
eign nam e are listed in T able 2.3.
TABLE 2.3 Elem ents with Sym bols Derived fro m an
Ancient or Foreign Name
C om m on N am e O rigin o f Sym bol Sym bol ^
an tim o n y stib iu m Sb
copper cuprum Cu
g o ld aunim Ли
ir o n fcrrum Fe
lead plu m b u m Pb
m ercury h y d ra rg y ru m Hg
p o ta s siu m kaliurn К
s ilv e r a rgentum Ag
sodium n a triu m Na
tin sta n n u m Sn
tu n g ste n w olfram W
V )

2 .S om e sy m b o ls arc ju s t the first le tte r o f the E n g lish n am e o f th e e le ­

m ents, as in the follow ing exam ples

B, boron H , hydrogen O , oxygen U, uranium

C , carbon I, iodine S, sulfur P , phosphorus
F , fluorine N , nitrogen Y, yttrium V, vanadium

3. M any sym bols are the first tw o letters o f the E n g lish nam e. E x am p les
are;
A l, aluminum B r, brom ine He, helium
Ca, calcium Si, silicon Ne > neon

4 . A few sy m b o ls are the first le tte r o f the E n g lish n am e and one o th e r

le tte r w h ich is n o t the second letter. T h is is b ecau se so m e elem e n ts h a v e the
n am es w ith the sam e first tw o letters. F o r exam ple,

Cs, cesium Cl, chlorine T l, thallium Z n , zinc

Cd, cadmium Cr, chromium T h , thorium Z r, zirconium
32 Chapter 2

EXA M P LE 2.5 S y m b o liz in g the E lem en ts

Problem: W hat is the chemical symbol for each of the following elements ?
(a) iron (b) silver (c) phosphorus (d) calcium (e) mercury (1) nickel
Solution : (a) Fe (b) Ag (с) P (d) Ca (e) Hg ( 0 Ni
—_— ,
EXERCISE 2.2 What arc the symbols for the following elements ?
(a) magnesium (b) manganese (c) cobalt (d) argon (c) silicon (f) beryllium

EXA M PLE 2.6 N a m in g the E lem ents

Problem : W hat is the name of each o f the following elements ?
(a) К (b) A1 (с) С (d) N (e)Ne (f)Na (g) 0 (h) Os (i) He
Solution : (a) potassium (b) aluminum (c) carbon (d) nitrogen (e) neon
(f) sodium (g) oxygen (h) osmium (i) helium

EXERCISE 2. 3 Give the names o f the elements for which the symbols arc ?
(a) H (b) Rb (c) Ba (d) Sr (c) S (f) Xe (g) F (h) Cl (i) Bi

2 .2 .2 FO RM ULAS
T h e formula for a com p o u n d is a sh o rth an d w ay o f w ritin g the nam e
fo r a co m pound. T h e ch em ical sym bols that are assig n ed to the elem en ts are
used to w rite form ulas. A chemical formula is a sym bolic representation o f
1. The elements present in a compound.
2. The relative numbers o f atom s o f each element.
C o n sid er the follow ing form ula fo r w ater. T h e elem en ts p resen t are d e­
n o ted by th e ir sym bols and the relative num bers o f atom s by subscript n u ­
m e ra ls.
I— I---------------- > tw o e le m e n ts p re s e n t
H 20 - » lack o f su b scrip t m ean s o n e atom o f О p e r fo rm u la u n it
1----------------- >tw o h y d ro g e n a to m s p e r fo rm u la u n it

A s show n above, the subscripts o f the fo rm ula indicate the relative n u m ­

b e r o f atom s o f each type that are com bined. I f a sym bol carries no subscript,
th e n u m b er 1 is accepted.
F o r exam p le, the fo rm ula o f su lfuric acid, H 2S 0 4 , in d icates th at tw o at­
om s o f h y d ro g en , one atom o f sulfur and fo u r atom s o f o x ygen are contained
in a fo rm u la u n it o f sulfuric acid. F o rm u las are also used to show the atom ic
c o m p o sitio n o f som e elem ents. A number o f elem ents occur in nature in dia­
tom ic m olecules. H 2, N2, 0 2, F2, Cl2, B r 2,1 2 are d ia to m ic e le m e n ta l m o le ­
cu les.S om e elem ents arc com posed o f m olecules containing m ore th an tw o at­
o m s such as P4 , Se.
 A Scientific M o d e l: Atomic Theory 33

C hem ical form ulas can be classified in three groups as follow s:

1. Simplest (empirical) formula : A fo rm u la that states the relative
num bers o f atom s o f each elem ent in the com pound is called the empirical
(or simplest) formula.
2. Molecular Formula : A m o le cu le is a p a rtic le fo rm ed fro m tw o
o r m o re atom s. S om e (but n o t all) co m p o u n d s o c c u r in m o le c u la r form . The
form ula that states the actual numbers o f atoms o f each elem ent in a molecule
o f the com pound is called the molecular formula. F o r ex am p le, the m o le c ­
u la r fo rm u la o f hydrogen p eroxide is H 20 2; the em pirical fo rm ula is H O .
T h e m o lecular and em pirical form ulas are the sam e for som e com pounds,
in clu d in g H 20 , C 0 2, HC1, N H 3, B F3, and H 2S 0 4. T h e m o lec u la r fo rm u la m ay
be a m u ltip le o f the em pirical form ula. F o r ex am p le, th e m o le c u la r fo rm u las
N 2H 4, C 6H 6, B 3N 3H 6 corresptTnft to the em pirical form ulas N H 2, C H , B N H 2.
3. Structural Formula : Tells w hich atom s are connected to w hich at­
oms, and how these are arranged in space. See T able 2.4 to com pare the types
o f form ulas.
TABLE 2.4 T ypes o f F o rm u la s f o r So m e C om pounds
' Name Simplest Formula Molecular Formula Structural Formula л

Water H20 H20 -О

H H

Ammonia NH3 NH3 н | н

н

н
Methane CH4 CH4
н — с — н
1
н

i н
Cyclopropane* CH 2 c 3h 6

f /С \ / н
с ----- с
п чн

н /Н
Ethylene* CH2 C2H4 с -с
'н '/ '" " и

EXERCISE 2.4 What arc the empirical formulas of each of the following
• i
a ) N 20 4 b ) C 6H 120 6 c ) C 8H 8 d) H - C - C = О

* S o le th a t d iffe r e n t .substances m ay h ave th e sa m e e m p iric a l fo r m u la B ut the m o le c u le s d iffe r in their m o le cu la r a n d s tru c tu r a l Jar

m u la s. ,
34 Chapter 2

2.3 CHEMICAL NOMENCLATURE

2.3.1 USING VALENCE RULES TO WRITE FORMULAS
In w ritin g the form ulas fo r m o st sim ple com p o u n d s, the fo llo w in g rules
are applied.
1. T h e m o re m etallic elem en t is w ritten first.T he m etallic elem ents are
th o se w h o se atom s ten d to lo se one o r m ore electro n s to form p o sitiv e ions
called cations.
2. T h e m o re n o n m etallic elem e n t is w ritten last.T h e n o n m eta llic atom s
tend to g ain one o r m ore electrons to form n egative ions, called anions.
3 . T h e n e t charg e on the resu ltin g com p o u n d m u st be zero. T h u s, the
c h arg es in d icated by the v alen ce nu m b ers m u st b e b alan ced . T o do this, su b ­
scripts are w ritten to the right o f the elem ent o r polyatom ic ion.
4. T h e valence o f a p o lyatom ic ion m u st eq ual th e algebraic sum o f the
charges assigned to the individual atom s m aking u p the p o lyatom ic ion.
5. I f a p o ly ato m ic ion appears m o re th an o n ce in th e fo rm u la, it is e n ­
clo sed in p aren th eses, and the sub scrip t is p laced ju s t o u tsid e to the right. See
T able 2.5 to recognize the valence num bers o f ions.
T h e fo rm u la fo r the co m pound form ed b e tw e e n th e ions X n+ and Y m',
m ay be w ritte n X n+ Y m" => X mY n if |nl = |m | th en the fo rm u la is sh o r­
tened to X Y
Look at the following examples:
Name of compound Charges of elements Formula of compound
Aluminum oxide A l3+ , 0 2- A120 3
Silver sulfide A g+ , S2- A g2S
Magnesium oxide M g2* , O 2' M gO (Iml = Ini)
Ammonium sulfate N H 4+ ,SO ^- (N H 4) 2S 0 4
Barium phosphate B a2+, POjf- Ba 3(P 0 4)2

EXA M PLE 2.7 Writing Chemical Formulas

Problem : W rite the correct formula of compounds formed between the following ions.
(a) Na+, and C f (b) Mg2+ and C f (c) Al3+, and O 2 (d) Mg2+, and N 3‘ (e) Pb4+, and O2’
(0 NH4+, and CN" (g) N H ;, and SO^- (h) Al3+- and S O |" (i) Fe3+, and O H '
Solution : (a) NaCl (b) M gCl2 (c) A120 3 (d) M g3N 2 (e) P b 0 2
(f) NH4CN (g) (NH4)2S 0 4 (h) A12( S 0 4)3 (i) Fc(OH)3

EXERCISE 2.5 Write the correct formula of the compounds formed between the corresponding cations
 A Scientific M o d e l: Atomic Theory 35

TABLE 2.5 F o rm u la s, C harges ( V alences) a n d N a m es o f S o m e C o m m o n Io n s

c л
+ 1 + 2 + 3 + 4 - 1 - 2 - 3
L i+ (lith iu m ) M g 2+ (m ag n e siu m ) A l 3 +(alum inum ) F" (fluoride) N 3" (n itrid e )
O 2’ (ox id e)
N a+ (sodium ) C a 2+ (calcium ) B i3+ (bism uth) С Г (c h lo rid e) P 3 " (p h o sp h id e )
S 2' (su lfid e)
IO N S

K + (potassium ) B a 2 +(barium ) C r3+ (chrom ium П1) B r ' (brom ide)

A g + (silv er) Z n 2+ (zinc) I" (io d id e )
MONATOMIC

H + (h y drogen) N i2+ (n ick e l)

F e 2+ (iron II) He3 ' (iro n III)
г у
C u + (copper I) C u 2+ (co p p er П)
H g + (m ercury I) H g 2+ (m ercury II)
P b4+ (lead IV )
P b 2+ (lead II)
S n 4+ (tin IV )
S n 2+ (tin II)
C o 2+ (c o b alt II) C o 3+ (cobalt Ш ) 4
(p e ro x id e )
H" (hydride)

sof
NH 4 (A m m onium ) O H "(hydroxide) P 0 34'
(su lfa te )
NO 3 (nitrate) (p h o s p h a te )
c o f
M n04 [F e(C N )6]3 “
(c a rb o n a te )
ION S

(p e rm a n g an a te) (ferric y an id e)
C r O\ -
С Ю 3 (c h lo ra te
(c h ro m a te ) - 4
POLYATOMIC

HCO 3 C r 2 0 2'
(b ic a rb o n a te ) (d ich ro m ate ) [Fe(C N )6]4"
CH 3 C O O ‘ c 2o l (ferro c y a n id e )
(acetate) (o x a la te ) S iC ^
IO j (io d ate) so | (o rth o silic a te )
CN" (cyanide) (su lfite )
s 2o |
(th io s u lfa te )
У
f

EXERCISE 2.6 Write the correct formula of the compounds formed between the corresponding cations
and anions.
r .....................
------------------
Io n s O xide Sulfide Iodide H ydroxide P hosphate C h ro m ate P erm an g an ate C arbonate

Sodium
S ilv e r
Z inc
A m m onium ■* '
-------------------- -----------------
C o p p e r (1)
- ................... ....... ......................
Iron (11)
Iron (III) ---------------- ------------------ ---------------- ...............
Lead (IV )
36 Chapter 2

2 .3 .2 N A M IN G C H E M IC A L C O M P O U N D S
2.3.2.1 METAL-NONMETAL COMPOUNDS
A) Binary compounds (compounds formed from two kinds
of atoms)
Salts o f a m etal and nonm etal are nam ed b y giving the nam e o f the m etal
first, and th is is fo llo w ed by the n am e o f th e n e g a tiv e io n form ed from the
non m etal, w hose ending is changed to " id e " .
|----------------------------------- n am e u n c h a n g e d --------------------- ^
N aC l sodium chloride
I----------------------------------- encjjng -------------------------------- J

N a m e o f m eta l + N a m e o f n o n m e ta l + "ide"

C heck the follow ing exam ples :

AI2O3 —> Aluminum oxide СаВгг —> Calcium bromide
AgCl —» Silver chloride MgS —> Magnesium sulfide
M an y m e tals, e sp e c ia lly tra n sitio n and p o st-tra n sitio n m e ta ls can be
fo u n d in co m p ounds in m o re th a n one ox id atio n state. In n am in g ions o f m e t­
als that can h av e m ore th an one ox id atio n state in com pounds, R o m an n u m er­
als are u se d to in d ica te the p o sitiv e ch a rg e (o x id a tio n state) o n the io n in a
com pound.
Fe2+ iron (II) Cu+ c o p p e r (I)
Fe3+ iron (III) Cu2+ c o p p er (II)
Cr2+ chrom ium (II) Hg 2 m ercury (I)
Cr3+chrom ium (III) Hg2+ m ercu ry (II)
W h e n th e co m p o u n d s o f the ele m en ts th a t h a v e v a ria b le ch a rg e s are
n am ed , th e ch arge o f th e m etal m u st b e w ritten in p aren th e se s in ro m an n u ­
m erals after the nam e o f the elem ent. E xam ine the follow ing exam ples.
I charge of m e ta l-------------- ^
FeO Iron (II) oxide
|________ name of m etal_______t

, charge of m etal_______
'I
РегО з Iron (II) oxide
I________ name of m etal________J4
& 2S3 Chromium (III) sulfide CuCl Copper (I) chloride

E X A M P LE 2.8 N a m in g C o m p o u n d s
Problem: Name the following compounds.
(a) M gCl2 (b) AlBr 3 (c) Li3N (d) С Ю (e) CaS (f) Al20
 A Scientific M o d e l: Atomic Theory 37

Solution: (a) Magnesium chloride (b) Aluminum bromide (c) Lithium nitride
(d) Calcium oxide (e) Calcium sulfide (f) Aluminum oxide

EXER C ISE 2.7 Name the following compounds.

(a) CrCI3 (b) CuO (c) Mn 20 3 (d) S n 0 2 (c) Hg 2CI 2 (0 PbS (g) FcCl 3 (h) Pbl 2
(b)Copper(II)oxide ( e )M ere u r y ( l ) c h l o ride

EXA M PLE 2 . 9 W ritin g F o rm u la s for C om p ou n d s

Problem : W rite the formulas of the following compounds.
(a) Calcium chloride (b) Zinc sulfide (c) Strontium fluoride
(d) Magnesium oxide (e) Silver chloride (0 Barium chloride.
Solution : (a) CaCl2 (b) ZnS (c) SrF 2 (d) MgO (e) AgCl (0 BaCl2

EXER C ISE 2.8 Write the formulas o f the following compounds

a) Magnesium bromide bt Aluminum sulfide c) Copper tlj chloride
d) Barium iodide c) Silver nitride f) Zinc fluoride
( h) , i /_>.S' ; <■) A fij.X

EXA M PLE 2 .1 0 N am in g C o m p ou n d s and W riting F orm ulas

Problem : Supply the missing information for the following compounds
(a) SnF2, .................................... ; (e) iron (III) sulfide................................. ,
(b) FeS.......................................... ; (0 tin (IV) chloride ...................................
(c) P b 0 2 , ..................................... ; (g) Lead (II) o x id e ......................................
(d) CuB r 2 ..................................... . (h) chromium (III) chloride;.........................
Solution: (a) tin (II) fluoride, (b) iron (II) sulfide, (c) lead (IV) oxide (d) Copper (II) bromide
(e) Fc 2S 3 (0 S n C l4 (g )P b O (h )C rC l 3

B .T e r n a r y C o m p o u n d s : A te r n a r y c o m p o u n d c o n sists o f th re e
d iffe re n t elem en ts. A co m m o n ty p e o f tern ary co m p o u n d in v o lv es a sim p le
m o n ato m ic (one atom ) ion and a p o ly ato m ic ion. A p o ly a to m ic ion co n tain s
tw o o r m ore atom s. ( S ee T ab le 2.5 ) In n am in g these com p o u n d s use th e fo l­
low ing pattern:
Name of metal + Name of Polyatomic ion
L o o k at the follow ing exam ples.
A 1(N 0 3)3 —> A lum inum nitrate C u C 0 3 -> C opper (II) carbonate
C aC 20 4 —> C alcium oxalate A g 3P 0 4 -> S ilver phosphate,
F e(O H )3 -> Iron (III) hydroxide B a S 0 4 —> B arium sulfate
38 Chapter 2
EX A M P LE 2.11 N a m in g C o m p o u n d s W h ic h C o n ta in P o ly a to m ic Io n s
Problem : Taj NaN 0 3 (b )C a C 0 3 (c)C a 3 (P O .) 2 (d) KC10 3 (c) Al 2 (S 0 4)3 (Ь K,C'r 20 7
Solution : (a) Sodium nitrate (b) Calcium carbonate (c) Calcium phosphate
________________ (d) Potassium chlorate_______ (e) Aluminum sulfate_________(I) Potassium Tichromate
EX A M P LE 2.12 W r itin g F o r m u la s for P o ly a to m ic Io n C o n ta in in g C o m p o u n d s .
Problem : W rite correct formulas for the following compounds.
(a) Iron (III) sulfate (b) Mercury (I) acetate (c) Ammonium nitrate
(d) Calcium bicarbonate (c) Lead (II) chromatc (f) Potassium permanganate
Solution : (a) Fe2 (S 0 4)3 (b) Hg 2 (C 2H 30 2)2 ( d M l .NO, (d) Ca (H C 0 3)2
ф PbCrO. (ft KM 11O.
EXERCISE 2.9 Supply the m issing information for the follow ing
(a) (N li 41,S ()л ................... (f) Sodium chrom aie....................
(b) NaOli .......................... (c) Calcium cyanitle .....................
(c) C u4( PO .i) 1 ................... (h) Potassium chlorate ................... '

(d) A h ( C ( h h ...................... ( 1) Potassium lerrocvanide ...................

(C) P M O ;h ......................... ifi Chromium 1111) nitrate .....................

C. H y d r a te s
Compounds that have a specific num ber o f w ater m olecules attached to
them are called hydrates. F o r ex am ple in C u S 0 4.5H 20 , 5 m o lecules o f w ater
rem ain attached to the one C 11SO 4 m olecule. In n am in g these com p o u n d s it is
helpful to use the pattern :

N am e of a n h y d ro u s T he prefix show ing the , ,

co m p o u n d + n u m b e r of w a te r m olecules + ny o r;ite

Som e o f the prefixes used to indicate the n u m b e r o f ions o r m olecules in

a form ula are given below.
Prefix M eaning Prefix Meaning
mono 1 (often omitted ) hexa 6
di 2 hcpta 7
tri 3 octa 8
letra 4 nona 9
p en ta . 5 deca 10

E x a m p le s -Ф
-Г
CaSCXiCl-bO —> calcium sulfate dihydrate
/s

NayCO}. 10H2O -» Sodium carbonate decahydrate(Washing soda)

MgS 0 4 .7H 20 -» Magnesium sulfate hcptahydrate (epsom salt)
CUSO4.5 H 2O —> Copper (II) sulfate pentahydrate (blue vitriol)
 A Scientific M o d e l: Atomic Theory 39

2 .3 .2 .2 N O N M E T A L -N O N M E T A L COMPOUNDS
W h e n tw o n o n m e ta llic e le m e n ts c o m b in e , n o io n s are
fo rm e d .H o w ev er it is gen erally p o ssib le to c o n sid e r one o f the tw o
elem ents to be the m ore m etallic. B oth in w riting the nam e and the for­
TABLE 2.6 Use o f Prefixes m u la o f a bin ary co m pound, the m ore m etallic e le m e n t ap pears first,
in N om enclature follow ed by the m ore nonm etallic one.

F o r m u la N am e -N a m e of nonm etal—
B C I3 B o ro n tric h lo rid e ionic name of nonmetal
CC14 C a rb o n te tra c h lo rid e Ji)i nitrogen pentoxide
N 20 5
CO C a rb o n m o n o x id e ^
prefix for the subscript
co 2 C a rb o n d io x id e
prefix for the subscript
NO N itro g e n m o n o x id e
no 2 N itro g e n d io x id e
E xam ples :
n 2o D in itro g e n m o n o x id e
N 2O 3 -» Dinitrogen trioxide
n 2o 3 D in itro g e n trio x id e
n 2o 4 D in itro g e n te tro x id e P4O 10 —» tetraphosphorus decoxide
n 2o 5 D in itro g e n p e n to x id e S 2CI2 —» disulfur dichloride
SF 6 S u lfu r h exafluoride
C 0 2 -» carbon dioxide
CO -» carbon monoxide the word mono at the be-
F o r oxid es, the "a" in the p r e ­
fix is u su a lly o m itted . F o r e x ­
a m p le w e w rite p e n to x id e
ra th e r th an p e n ta o x id e
NO -» nitrogen monoxide
CCI4 -> carbon tetrachloride } gining of the name is
generally om itted.

EXA M PLE 2.13 N a m in g N o n m eta l-N o n m eta l C o m p o u n d s

Problem : Name the following compounds
(a) ICIq (b) BrF 5 (c) AsCl3 (d) SF4 (c) PCl 3 (f) S 0 3
Solution : (a) Iodine trichloride (b) Bromine penlafluoridc (c) Arsenic trichloride
________________(d) Sulfur tetrafluoridc_______(c) Phosphorus trichloride________ (f) Sulfur trioxide______
E X A M P LE 2.14 W ritin g F o rm u la s for C om p o u n d s
Problem : Write correct chemical formulas for the following
(a) Chlorine dioxide (b) Silicon tctrafluoride (c) Diboron tetrabromidc
(d) Tricarbon disulfide (e) Iodine pcntafluoride (0 Tetraphosphorus trisulfide
S o lu tio n : (a) CIO, (bl SiF. (c )B ,B r. (dl C ,S , (e) IF, (0 P .S ,
EXERCISE 2.10 Name the following compounds using prefixes when needed.
a )P C l5, b ) S 0 2, c) C l 20 7, d )S iQ 2, c) N 2Q 5, Q CIF3, g ) P 40 ; o :
E XER C ISE 2.11 Supply the missing information for each of the following
(a) Sodium nitrate (0 Cobalt (II) sulfate................ (к) КМПО 4............. (p) MgCl 2.6H 20 ............
(b) Potassium carbonate... (g) Lead (IV) acektic................. (I) P b C r0 4.............. (r) Si2F 6.........................
(c) Silver phosphate (h) Sodium sulfate decahydratc.... (m) F c P 0 4............... (s) Р4О б.......................
(d) Sodium thiosulfatc ( 1) Phosphorus tri brom ide (n) (NH 4) 2Cr 20 7 ...... (t) C120 ........................
(e) Potassium fcrricyanidc. (j) Dihydrogcn monoxide (o) F e S 0 4.7H20 ...... (u) CBr 4.......................
40 Chapter 2

2.4 RELATIVE ATOMIC WEIGHTS

E v en th o u g h it has n e v er been p o ssible to m easure the w eig h t o f a single
atom o f an elem en t o r a single m olecule o f a co m p o u n d , it is p o ssib le to find
the w eights o f equal nu m b ers o f different atom s o r m o lecu les. A s a result, w e
can obtain the relative w eights o f individual atom s o r m olecules. F o r exam ple,
12.000 g o f C -1 2 c o n ­
by w eig h in g th e equal n u m b e r o f hy d ro g en , o x y g en , and m ag n esiu m atom s,
tain s 6 .0 2 x l0 2 3 С atom s.
w e can find th at the o x y g en atom s w eigh ap p ro x im ately 16 tim es as m u ch as
So the m ass o f one С
atom is
th e h y d ro g en atom s, and tw o -th ird s as m u ch as the m ag n esiu m atom s. T hus,
o x y g e n w as a ssig n ed a relativ e m ass o f a p p ro x im ately 16, and w as used as
12.000 , i n -23
------------- — = 1 .9 9 x 1 0 g th e referen ce ele m en t fo r assig n in g ato m ic w eig h ts o f all th e ele m en ts until
6 .0 2 x 1 0
1961.T o d a y a p a rtic u la r ty p e o f c a rb o n atom (w h o se relativ e ato m ic w eig h t
and :
w as accep ted as 12.00000) is used as the stan d ard . (S ee b a ck c o v e r fo r the
1 amu = — x 1 .9 9 x 1 0 . relative w eights o f atom s o f the elem ents.)
12
-24 T h e actual m asses o f atom s are very sm all. T h e m ass o f any atom can be
1 amu = 1 .6 6 x 1 0 g
e x p re sse d as th e re la tiv e ato m ic w eig h t in u n its o f am u. (a m u = a to m ic
or
m a ss u n it, w h ich is 1/12 the m ass o f one carb o n - 12 atom .). W h en the re la ­
l g = 6 .0 2 x l 0 2 3 am u tive ato m ic w eig h t o f an elem en t is given in units o f gram s, it is k n o w n as the
_________________________ g r a m a to m ic w e ig h t.____________________________________________________
EXA M P LE 2.15 F in d in g A to m ic W e ig h t
Problem : The ratio of the mass of oxygen atom to carbon atom is 1.3329. What is the mass of the oxygen
atom ?
Solution : The ratio o f the masses is oxygen/ carbon = 1.3329
The mass of oxygen atom is 1.3329 times the mass o f carbon atom.
Mass of oxygen atom = 1.3329 x 12.00000 = 15.9948

EXERCISE 2.12 T he ratio o f.th e m ass o f brom ine atom to carbon is 6.650. W hat is the m ass o f the
brom ine atom ?

A fo rm a l d e f in itio n o f 2.5 MOLE CONCEPT AND AVOGADRO’S NUMBER

m o le a cc o rd in g to S I is :
A ny sam ple o f m atter w e exam ine contains a very large n u m b er o f atom s
T h e a m o u n t o f any s u b ­
s ta n c e th a t c o n ta in s as o r m olecules. W e n e v er w ork w ith individual atom s o r m o lecu les b u t w ith the
m a n y e le m e n ta ry e n titie s c o llectio n o f th ese p articles. T h e relative w eights o f atom s, m en tio n ed in the
as the n u m b e r o f ato m s preced in g section, contain the sam e n u m b er o f atom s. T his n u m b er is called as
in 0 . 0 1 2 k g o f c a rb o n - A v o g a d r o 's n u m b e r. T h e v alu e o f A v o g a d ro 's n u m b e r h a s b e e n e x p e ri­
12 v
m en ta lly d eterm in ed to be 6.022 x 1023. T h e larg e size o f A v o g ad ro 's n u m ­
b er indicates th at atom s and m olecules m u st b e extrem ely tiny.
The am ount o f a substance that contains Avogadro's num ber o f elem en­
tary units is called a m ole * (abbreviated mol).
W h en an en tity is ex p ressed in m oles, the k in d o f en tity m u st be stated
too. F o r ex am p le it is am biguous to say 1 m ol o f o x ygen, b ecau se it is clearer
to say 1 m ol oxygen atom o r 1 m ol o x ygen m olecule.
T h e m ole, although it contains enorm ously large n u m b er o f entities, rep-
Gram-alomic weight, gram formula weight, gram ionic weight are frequently used instead o f mole.
 A Scientific M o d e l: Atomic Theory 41

resents a sp ecific number, like the words, "pair" or "dozen" or "lira". Just as a
dozen contains 12 item s, a m ole contains 6 .02 x l 0 23 item s, w h ich m ay be ele ­
T h e m ole n u m b e r (n ) o f
m ents, m olecules, ions or other entities.
a sam ple o f m a tte r c o n ­
tain in g N e n titie s m ay For e x a m p le: r
be fo u n d b y the form ula:
6 .02 x l 023 pencils = 1 m ol pencil
_ N (e n titie s )
6 .0 2 x 1 0 23 С atoms = 1 m ol С atom
N a ( e n titie s /m o le )
6 .02 X1023 O 2 m olecules = 1 m ol O 2 m olecule
6 .0 2 x l0 23 H 2O m olecules = 1 m ol H20 m olecule
6.02x10 23 H+ ions = 1 m ol H+ ion
EXA M P LE 2.16 Calculating Mole Number
Problem : Calculate the number o f moles of each o f the following
a) 3.01xl0 22 N 2 molecules b) 4 .8 2 x l0 24 iron atoms
Solution :
a) 6 .02 x l 023 N 2 molecules 1 mol N 2 molecule 'i 22
3.01x10
= 0.05 mol N 2 molecules
3.01xl0 22 N 2 molecules___________ x_______ J 23
6 .02x 10
24
b) 6 .0 2 x l0 23 Fe atoms 1 mol Fe atom 4.82x10
x - = 8 mol Fe atom
4 .8 2 x l0 24 Fe atoms x mol Fe atom 23
6 .02 x 10

Another approach to problem solving is to use the dimensional analysis method. Now let us examine how to use
this method in solving the problem in example 2.16. Consider the proportionality
if 6 .02 x l 023 N 2 molecules are in 1 mol N 2
3.01xl0 22 N 2 molecules x_________ 23

In this method the first line o f the proportionality is written as a fraction either like 6.02x10—N 2 molecules^
1 mol N 2
1 mol N 2
or ----------- - ------------------- and the item in the second line as a factor to this fraction.
6.02x10 N 2 molecules

To decide which is going to be used we will treat the units as algebraic quantities and do the unit cancellations
correctly. The unit of the result must be mol so we have to choose the one which gives "mol" after the unit can­
cellations have been done. You should recognize that the numerator of the fraction must be the desired unit (mol)
and the denominator o f the fraction must be the given unit (number of molecules)

Given unit x un' 1 = desired unit => 3.01x10 N jm olcculcs x ---------- 1 mol N 2 = 0.05 m ol N 2
G,Ve" Un,t 6.02x10s N jfflotm te

It can be seen that the units o f N 2 molecules cancel, leaving only mol N 2, the desired unit. Since a measured
quantity is meaningless unless its units are specified, then units must be carried through all calculations. If units
are treated as algebraic quantities, the unit of the result will indicate whether the calculation has been carried out
correctly.
b) 4 .8 2 x l0 24Fe-atom s x 1 molaFe atom = 8 mol Fe atom
6.02x10 Fe-atoms
 A Scientific M o d e l: Atomic Theory 41

resents a sp ecific number, like the words, "pair" or "dozen" or "lira". Just as a
dozen contains 12 item s, a m ole contains 6 .02 x l 023 item s, w hich m ay be e le ­
T h e m ole n u m b e r (n ) o f
m ents, m olecules, ions or other entities.
a sam p le o f m a tte r c o n ­
tain in g N e n titie s m ay For e x a m p le : r
be fo und b y the form ula:
6 .02 x l 023 pencils = 1 m ol pencil
n _ N (e n titie s )
6 .0 2 x l0 23 С atoms = 1 m ol С atom
N a ( e n titie s /m o le )
6 .02 X1023 0 2 m olecules = 1 m ol 0 2 m olecule
6 .0 2 x l0 23 H20 m olecules = 1 m ol H20 m olecule
______________________________ 6.02X10 23 H+ ions = 1 m ol H+ ion______________
EXA M PLE 2.16 Calculating Mole Number
Problem : Calculate the number of moles of each of the following
a) 3.01xl0 22 N 2 molecules b) 4.8 2 x l0 24 iron atoms
Solution :
a) 6.0 2 x l0 23 N 2 molecules 1 mol N 2 molecule -* — - 22
3.01x10
x = = 0.05 mol N 2 molecules
3.01xl0 22 N 2 molecules
б Ш х Ю 23

24
b) 6 .0 2 x l0 23 Fe atoms 1 mol Fe atom
4 .8 2 x l0 24 Fe atoms x mol Fe atom } x = ——— —
6 .02 x 10
23
= 8 mol Fe atom

Another approach to problem solving is to use the dimensional analysis method. Now let us examine how to use
this method in solving the problem in example 2.16. Consider the proportionality
if 6.0 2 x l0 23 N 2 molecules are in 1 mol N 2
3.01xl0 22 N 2 molecules x_ a
In this method the first line o f the proportionality is written as a fraction either like —I 2_________
1 mol N 2
1 mol N 2
or ------------- and the item in the second line as a factor to this fraction.
6.02x10 N 2 molecules

To decide which is going to be used we will treat the units as algebraic quantities and do the unit cancellations
correctly. The unit of the result must be mol so we have to choose the one which gives "mol" after the unit can­
cellations have been done. You should recognize that the numerator of the fraction must be the desired unit (mol)
and the denominator of the fraction must be the given unit (number of molecules)

Given unit x un'1 = desired unit => 3.01x10 N 2molecules x ---------- 1 mol N 2 = 0.05 m ol N 2
G ,v en u n “ 6 .1Ы 0 я ) М » 1« ь

It can be seen that the units of N 2 molecules cancel, leaving only mol N 2, the desired unit. Since a measured
quantity is meaningless unless its units are specified, then units must be carried through all calculations. If units
are treated as algebraic quantities, the unit of the result will indicate whether the calculation has been carried out
correctly.

b) 4 .8 2 x l0 3>Fe-atom s x 1 mol, J e atom = 8 mol Fe atom

6.02x10 Fc atoms
42 Chapter 2

From now on we will use these two methods in problem solving interchangeably

E X E R C IS E 2 .1 3 Perform the \ . intereonvcrsions of mote and particai number.

f hi 2 m ol 0 2 m o le c u le s = ? ( Ь m o le c u le s (d) 0 .2 5 m ol H ^ ions - .’ H ' ions

(и) 0. 1 , h ) l . 2 x l 0 24 in 20 u .v lir :

EXAM PLE 2 .1 7 U n d e r s ta n d in g M o le C o n c e p t
Problem : How many years does it take to evaporate all the molecules in one millimole of water if six bil­
lion water molecules evaporate in each second ?
Solution : To understand the reasoning in the solution of this problem examine the following solution
chart:
Step I. 1 mmol H20 —> ? mol H20 —> ? H20 molecules
1 mmol H20 = IxlO "3 mol H20 = lx lO "3 x 6.02xl0 23 H20 molecules => 6 .0 2 x l0 20 H20 molecules
Step II. Let us find the number of seconds in which 6 .02xl ()20 H20 molecules evaporate
23 1 <, 11
6.02x10 H 20 molecules x --------------
9
= 1.0x10 s
6x10 H 20 molecules
Step III. Now let us change l.OxlO 11 s to years.
1 year = 365 days = 365x24 hours = 365 x 24 x 3600 seconds => 3 .2xl0 7 s

1.0x10 s x ■■1 yeaf? = 3,125 years = 3.1x10 years

3.2x10 s

E X E R C I S E 2 .1 4 if you had one mol o f T urkish Lira to divide am ong all the people in the w orld, how
much each o f the inhabitants would rccicve ? A ssum e the w orld's population is 6 billion in 1990.
______________________________________________________________________________________ 77. I . o o x i o 14
EXAM PLE : 2 .1 8 I n te r p r e ta tio n o f F o rm u la s in T e rm s o f M oles.
Problem : Answer these questions for 0.25 mol of Al20 3.Find
(a) The number of molecules it contains.
(b) The mole number of each kind of atom it contains
(c) The total number of atoms it contains.
Solution :
(a) 1 mol A120 3 6.0 2 x l0 23 molecules
| x = 1.51xl023 molecules
0.25 mol A12Q 3 x ____________
(b) The subscripts in a molecular formula of a compound show the number of the preceding atoms.
1 molecule of A120 3 contains 2 atoms of A1 and 3 atoms of О atoms. If we consider 1 mol of A120 3 molecules
then the subscripts show the mole numbers of the preceding atoms. In other words one mole o f A120 3 contains
two moles o f A1 and 3 moles of О atoms.
 A Scientific M o d e l: Atomic Theory 43

Thus • 9 mol A1
0.25 mol A120 3 x z m o l.AI - = 0.5 mol A1
1 mol A12 0 3

0.25 m ol A12 0 3x 3 m.°.1 9 — =0.75 mol О atoms

1 mol A120 3
(c) In 0.25 mol o f AI2O 3 there are (0.75+0.5=1.25) mol o f atoms totally. The number o f atoms in 1.25 mol is
2
, лс , , 6 .02 x 10 atoms п „ „
1.25 mol atom x --------------------- = 7.53x10 atoms
1 mol atom

EXER C ISE 2.15 Answer these questions for 2.4x10 24 SO 3 molecules. Find
(a) Its mole number (b) The number of moles of S and О atoms it contains
(c) The total num ber o f atom s it contains. (a) 4 ( b ) 4, 12 (с) 9.6X1024

v
2.5.1
t
A T O M IC M A S S OR A T O M IC W E IG H T *
T he w eight in grams o f 1 m ol (6 .0 2 x l0 23) atom s o f an elem ent is called
the atom ic w eight o f the elem ent. T he unit o f atomic w eight (usually abbrevi­
ated A W ) is g/mol.
For ex a m p le :
6.02X1023 С atoms = 1 m ol С atom = 12 g => A W o f С = 12 g/m ol
6 .0 2 x l0 23 Au atoms= 1 m ol Au atom = 198 g => A W o f Au = 198 g/m ol
I f m is th e m ass o f a Just as one dozen plum s do not w eigh the sam e as one dozen apples, 1
s in g le ato m , m ol o f С atom does not w eigh as much as 1 m ol o f Au atom.
_ AW (g /m o l)
R em em ber that atom ic w eigh t refers to the m ass o f 6 .0 2 x l0 23 atom s.
N a (a to m /m o l)
The actual m ass o f a single atom is obtained dividing the atom ic w eigh t by
A vogadro's number.
T h ere is n o n e e d to For exam ple the atomic w eight o f oxygen is 16 g/m ol. The actual weight
m em o rize the atom ic
o f an oxygen atom is :
w eig h ts o f e le m en ts.
T h ey are liste d in If 6 .0 2 x l0 23 О atoms 16 g 16 -23
= 2.67x10 g/atom
b o o k s. W h e n e v e r n e ­ 1 О atom x
cessary y o u m ay c o n ­
6 .02 x 10
su lt the lis t a n d u se
th e m . T he relationship betw een the atom ic w eight and m ass o f an elem ent is
given by the equation.

mole number = §ivet| weight n(moi) _ ™..... .

Atomic weight AW (g/mol)

* Even though mass and weight refer to the different properties of matter it is a common practice among chemists to say atomic
weight in the meaning of atomic mass
44 Chapter 2

E X A M P L E 2.19 In te r c o n v e r tin g M a ss - M o le - P a r tic le N u m b er

Problem : Answer these questions for 26 g of chromium. Calculate
(a) the mole num ber of atoms it contains
(b) the number o f atoms it contains
(c) the mass of a single chromium atom
(The atomic weight of chromium is 52 g/mol. In problems the atomic weight of an element is usually given as
Cr = 52)
Solution :
(a) The atomic weight, 52 g, is the mass o f 1 mol chromium atom.
If 52 g chromium has 1 mol Cr atom 2g
26 g chromium________ x________ J x = — = 0.5 mol Cr atom

Or, we may use the formula n=-^-, n =— — = 0.5 mol Cr atom

AW 52 g/mol

(b) Since 1 mol o f any entity contains 6 .0 2 x l023 entities, then the number o f atoms in 0.5 mol of Cr is :
23
лс . 6.02x10 Cr atoms ? А1 ,
0.5 mol Cr atom x --------------------------- = 3.01x10 Cr atoms
1 m ol Cr atom

Or remember n = -У- => N = n x N A = 0.5 x 6.02x10 = 3.01x10 Cr atoms

Na
(c) The atomic weight, 52 g, is actually the weight of 6.02xl023 Cr atoms. The weight of just a single Cr atom
is :
6.02x1023 Cr atoms 52 g v — -23
1 Cr atom x J x = ----------- —= 8.64x10 g
------------------------------------------------- 6.02x10

O - - " T - г - ------------------- = 8.64x10 23 g/atom

A 6.02x10 atom/mol

note : Pay attention to the differences between atomic weight and the actual weight of an atom.

EX E R C IS E 2.16 Perform the following conversions

(a) 3.2 g Cu = mol Cu (Cu = 64 g/mol)
(b) 0.2 mo! Ag = . g Ag (Ag = 108 g/inol)
(c) l silver atom = ...?... g
(d) 3 .0 1 x l0 22 Fe atoms = ...?... mol Fe atom = g Fe (Fe = 56 g/mol)
(e) 6.4 g S atom = mol S atom = ...?... S atoms. (S = 32)
______________________________ ( a) 0 . 0 5 mol ( b) 21.6 к ( с) 1.79x10'~2 у (d) 2 . 8 ,ц (e) / . 2 x 1 0~ 1 a t о in
E X A M P L E 2 .20 C o m p a rin g . M asses
Problem : List the following species in order o f increasing mass.
(a) 1 mol С atom (C=12g/mol) (b) 1 g of С (с) 1 carbon atom (d) З.ОШ О 23 С ai. -ms
Solution : To compare the masses, we should express the mass equivalent of matter in each choice.
(a) 1 mol С = 12 g С
(b) 1 g С = 1 g С
12 -23
(c) 1 carbon atom = -------------- = 2 x 10 g у The order of increasing mass is
23
6 .02 x 10 c<b<d<a
(d) З.01х10 23 С atoms = 0.5 mol С atom = 0.5x12 = 6 g С
 A Scientific M o d e l: Atomic Theory 45

EXERCISE 2.17 Which one oi (he following is (he heaviest

E X A M P L E 2 . 2 1 C a lc u la tin g th e M a ss P e r c e n ta g e o f a M ix tu r e
Problem : A 0.6 mol mixture of calcium and carbon elements weighs 10 g. Find the mass percentage of Ca
in the mixture ? С = 12, Ca = 40
Solution : Let x be the mole num ber of Ca in the mixture, then the mole number of С is 0.6-x
E lem ent mole mass (m=nxAW)
Ca x x.4 0
С 0.6-x + (0.6-x)xl2

40x + (0.6-x)xl2 = 10 => x = 0.1 mol (the mole num ber o f Ca)

a 1 i r^ a , i 40 g и о 10 8 mixturc 4 g Ca ^ ,
0.1 mol of Ca = 0.1 mol x s— = 4 g C a 1ПП . I r _ 4a „ 4 a c l п я hv m a s s
1 mol Ca 100 g mixture x J * - w g => 4U % u a oy mass

EXERCISE 2.18 50 % of by mass of a 2.2 mol mixture of He and Ar gases is He. Calculate the mole
number of He in the mixture ? He = 4, Ar = 40 2 mol

2.5.2 MOLECULAR W E IG H T

T h e w eight in gram s o f 1 m ol m olecules o f a com pound is called the m o ­

le c u la r w eig h t (ab b rev iated M W ) o f the com pound. Its u n it is g/mol. F o r e x ­
am p le 1 m o l o f H 2O m o lecu les ( 6 .02 x l 023 H 2O m o lecu les) has a w e ig h t o f
18 g. F o r th at reason the m o lecu lar w eight o f H 20 is 18 g/m ol.
T h e m o lecu lar w eight o f a com pound is the sum o f the atom ic w eights o f
the elem ents that constitute one m ole m olecule o f the com pound.
F o r exam ple ; let us find the m o lecu lar w eig h t o f H 20 (H = 1, О = 16)

1 m ol H20
I— > 1 m ol О => 1 x 16 = 16 g O
^ 2 m ol H = > 2 x 1 = 2 g H

T h e m olecular w eight o f H 20 => 18 g/m ol

T h e m o lecu lar w eight o f Са(7ЧОз)2 is therefore: (C a=40, N = 14, 0 = 1 6 )

1 m ol С а (Ж )з )2
I 1 ^ 6 m o lO = > 6 x 16 = 96 g
51 2 m ol N => 2 x 14 = 28 g
* 1 m ol C a => 1 x 4 0 = 4 0 g
______________________________________________________________________ 164 g/m ol____________________
E X A M P L E 2.22 Calculating M olecular W eight o f a C om p ou n d
Problem : Calculate the Molecular weight o f each of these compounds.
(a) C 0 2 (b )C a 3( P 0 4)2 (c) C u S 0 4.5H20 (d) Fe(NH 4) 2(S 0 4) 2.6H20
H = 1 , С = 12, N = 14, О = 16, P = 31, S = 32, Ca = 40, Fe = 56, Cu = 64
46 Chapter 2

Solution :
(a) CO 2 = 1x12+2x16=44 g/mol
(b) Ca 3( P 0 4)2 = 3x40+2x31+8x16=310 g/mol
(c) C u S 0 4.5H20 = 1x64+1x32+4x 16+5(2x 1+ lxl6)= 250 g/mol
(d) Fe(NH 4) 2(S 0 4)2.6H20 = Ix56+2xl4+ 8xl+2x32+8xl6+6(2xl+1xl6)=392 g/mol

EXERCISE 2.19 Calculate the molecular weights of the following compounds (Consult the table for
atomic weights) (a) N 20 5 (b) H2S 0 4 (c) Al(OH )3 (d) K A l(S0 4) 2.12H20 (c) Fc 4[Fe(CN )6|3
( a) 1 0 8 g / m o l (b)98g! m o l (c)78g/mol (d)474g/mol (e)860g/mol

E X A M P L E 2.23 C a lc u la tin g M o le N u m b e r o f C o m p o u n d s
Problem : Calculate the mole number o f each of the following compounds
(a) 15.2 g N 20 3 (N=14, 0 = 1 6 ) (b) 17.1 g A12(S 0 4)3 (AI=27, S=32) (c) 87.6 CaCl 2.6H20 (Ca=40, Cl=35.5)
Solution : (a) The first step is to calculate the molecular weight of N 20 3.
N 20 3 = 2x14+3x16=76 g/mol
We then find the mole number
1 mol N 20 3 76 g 1 _ 1 5 .2 _ n ~ . XT 0
x mol N 20 3 15.2 g ) - ° - 2 m o l N p 3l

Or we may use the formula, n(mol) = ПТ® to find the mol number : n = ~-l— = 0.2 mol N 9 O 4
MW (g/mol) 76 g/mol

(b) A12(S 0 4)3 = 2x27+3x32+12x 16=342 g/mol => n= 17Л s = 0.05 mol A12(S 0 4)3
342 g/mol
(c) CaCl 2.6H20 = 1x40+2x35.5+6x18=219 g/mol =» n = —87'6 g = 0.4 mol CaCl 2.6H20
219 g/mol

EXER C ISE 2.20 Perform the following conversions

(a) 8.8 g NaOH = .... mol NaOH (b) 0.05 mol C a 3(P 0 4)2 = .... g Ca 3( P 0 4)2
(c) 2.4x10 23 ICO molecules = .... mol H20 = .... g H20
(d) 17.16 g Na 2CO 3.10H2O = .... mol Na 2CO 3.10H2O = .... Na 2C 0 3.1()H20 molecules
(a)0.22m ol (b)I5.Sg (c)0.4m ol, 7 . 2 g ( d ) 0 . 0 6 m o l , 3 . 6 x I 0 22 m o l e c u l e s

E X A M P L E 2.24 U n d e r s ta n d in g M o le C o n c e p t
Problem : These problems refer to dinitrogcn pentoxide, N 1O 5 . (N = 1 4 ,0 = 16)
(a) Calculate the molar mass (b) Find the mass of 1.25 mol N2Cs
(c) How many moles of N 2Os are there in 5.4 g of compound?
(d) Calculate the mass o f compound that contains 0.5 mol o f oxygen atom.
(e) Calculate the mass o f compound that contains 6.4 g of oxygen.
(0 Find the mass o f N combined with 32 g of oxygen.
(g) Calculate the num ber of N atoms in 21.6 g of N 2O 5.
Solution : (a) M olar mass = The mass of 1 mol compound = M olecular weight
N 20 5 = 2x14+5x16=108g/mol

(b) n = -!H _ => m = n x MW => m = 1.25 mol x = 135 g

MW 1 mol
 A Scientific Model : Atomic Theory 47

.(C) n = - g - = 5 -4 ё . a 0 .Q5 mol N 2O s

MW 108 g/mol

(d) 1 mol N 20 5 has 5 mol О | x = о л mol N 20 5=> 0.1 mol N 2O s x — M l ----= 1 0 . 8 g N 2O 5

x mol N2C>5 has _ 0.5 mol О ' 1 mol N 2O s

or since 1 mol N 2C>5 (108 g) contains 5 mol of О we may find the result in one step

0.5 mol О x f ^ 8 g N 2 ° | = 10.8 g N 2 O s

5 mol О

108 g N , 0 ,
(с) 1 mol N 20 5 (108 g) contains 5 mol О (5 x 16 = 80 g O) => 6,4 с О x — ------- = 8.64 g N 2 0 5
80 g О
(I) 1 mol N 20 5 is formed from 5 mol О (80 g) and 2 mol N (28 g) => 32 g О x = 11.2 g N
oO g О

(g) 1 mol N 205 (108 g) contains 2 mol (2x6.02xl023) N atoms =>

21.6 g N { ) 5x 2 x 6 -(12 x 10 N. uloms = 2.4 x 10 25 N atoms

108 g N p s

EXER C ISE 2.21 A nsw er the follow ing questions for C 0 2. Find
(a) its m olecular w eight (b) the m ass ol 1.25 mol o f C O ,
(c) the m ole num ber in 17.6 g 'o f com pound (d) the num ber of m olecules in 6 .6 g o f C 0 2
(c) the m ass o f С com bined with 0.25 molО (Г) the mol num ber o f О com bined with 2.4 g С
(g) the num ber o f О atom s in 35.2 g C 0 2 (It) the num ber of С atom s com bined with 20 oxygen atom s.
( a ) 4 4 f ’l m o l (1>)55ц ( c ) 0 .4 m o t ( d ) 9 x l ( f ~ m o le c u l e s (e)l.Sg ( )')(>.4 m o l ( g ) 9 . 6 x I l t ~ 3 a to m s
( h ) I 0 a t o in v

E X ER C IS E 2.22 3 mol m ixture o f S 0 2 and C O gases w eigh 120 g. Find the m ole num ber o f each gas
in the m ixture ? (C = 12, О = 16, S = 32) (U se the sam e procedure in exam ple 2.21) / m ol S O 7, 2 moI CO

the m ole num ber o f V L

2 .5 .3 M O L A R V O L U M E
o f a gas at STP is
The volum e occupied by 1 m ol o f a substance is called its molar vol­
, 2 V (L) ,
' 2 2 .4 ( L /m o l )
ume. E ven though the m o la r volum es o f solids and liquids change from su b ­
stan ce to su b stan ce, the m olar volumes o f all gases are the sam e under the
same conditions o f tempera ture and pressure. 1 m ol o f any gas occupies 22.4
for gases at STP : L at 0°C temperature and 1 atm pressure. 0°C and 1 atm pressu re are know n
m N 4
as Standard T em perature and P ressure (abbreviated S T P )
MW 2 2 .4 1 m o l H 2 = 6 .0 2 x l0 23 H 2 m o lecules = 2 g H 2 = 22.4 L at S T P
1 m o l C 0 2 = 6.02 x 10 23 C 0 2 m olecules = 44 g C 0 2 = 22.4 L at STP

E X A M P LE 2 .25 C alcu latin g M olar V olu m e

Problem : What is the volume of each of the following gases at S IT ?
(a) 0.25 mol S 0 3 (b) 35.2 g C 0 2 (c) 1.2xl0 24 H 2 molecules
Solution :
(a) At STP, 1 mol of any gas occupies 22.4 L 1 mol S 0 3 22.4 L
5.6 L
0.25 mol SO 3 x L
48 Chapter 2

(b) n co = - ™_ = 35-2 ё = 0.8 mol C 0 2=> 0.8 mol C 0 2x - 2M .k .,_ = 17.92 L C 0 2

MW 44 g/m ol 1 mol C 0 2

24
(c) n „ = — = -----1-2x10 molecules = 2 m 0, 2 mol . 2 2 -4 .L _ 44 g L щ
6 .02 x 10 molcculcs/mol ^ Ш°*

EXER C ISE 2.23 Perform these conversions

(a) 2 mol N 2 = .... L (at STP) (c)5.6 L 0 2 at STP = mol 0 2 = .... g 0 2 = .........0 2 molecules
(b) 6.8 g NH 3 = L (at STP) (d)4.8x10 s2 H 2 molecules = .... mol H 2 = L H2 = g H2
( a) 44.8 ( b) 8.96 ( c) 0.25,8 (d ) 0.08,1.8 L

EXAM PLE 2 .26 Calculating Density of a Gas at STP

P r o b l e m : Calculate the density at STP of each of the following gases
(a) 0 2 (b) Cl 2 (c) S 0 3

S o l u t i o n : d = — , if one mole of a gas is considered at STP then: m = MW and V = 22.4 L => d = MW g/mol
V 22.4 L/mol

(a) M W 02= 32 g/mol d= 3 2g/ mo1, = 1.43 g/L

2 22.4 L/mol

(b) M W C4=71 g/m ol d= 71/ / " fl()1T = 3.17 g/L

2 22.4 L/mol
(c) MW s o - 80 g/mol d= = 3.57 g/L
3 22.4 L/mol

- - - - - - .............

EXER C ISE 2.24 The density of the gas X at STP is 2.50 g/L. W hat is the molecular weight of the gas
X ?______ 56 g/mol

2.6 INTEGRATION OF MOLE CONCEPT

Because o f the great im portance o f the m ole concept in chem istry some
w orked-out problem s are given below . Be sure that you should be able to
solve these problem s w ith the know ledge you have had so far. These prob­
lem s are given to you to have an opportunity to check yourself. A very short
solution of the problem is introduced.

E X A M P L E 2 .2 7 C alcu latio n s B ased on M ole C oncept

Problem : How many atoms o f nitrogen arc there in 0.1 mol of C a(N 0 3)2 ?
Solution : 0.1 mol C a (N 0 3)2 -> ? mol N -> ? N atoms
0.1 mol Ca(NOj)2x — 2 mo1 N x 6'02 x — — at()ms. = 1.204X1023 N atoms
lm o lC a(N 03)2 1 mol N

EXER C ISE 2.25 W hat is the mass of (NH 4) 2S 0 4 that contains Avogadro's number of hydrogen atoms.
( N H 4 ) 2 S 0 4 = 132 g/m ol. 16.5 g

E X A M P L E 2 .2 8 Using Mole Concept to Calculate the Mass

Problem : How many grams of C a(N 0 3)2would you need to take to get 1.00 gram o f calcium ?
(Ca = 40, N = 14, О = 16)
 A Scientific M o d e l: Atomic Theory 49

S o lu tio n : 1 g Ca —> ? mol Ca — > ? mol Са(НОз)2 -» ? g Са(ЫОз)2

x U m jb G a^ 164gC aC N O ^
" 40-g-Ca-- 1 mot-Ga- 1 m o tC a fN O ^ ^ fe

E X E R C I S E 2 . 2 6 What is the mass of Na2S2C>7 that contains 5.6 g of oxygen ? N328207 = 222 g/mol
_____________________________________________________ . 11.1

E X A M P L E 2 . 2 9 Finding the Number of Molecules in a Given Mass

P r o b l e m : How many N2O5 molecules are there in 1.08 g of N2O5 ? (N = 14, О = 16)

S o l u t i o n ; 1.0 8 g N 2O5 — > ? mol N2O5 — > ? molecules of N2O5

, ^ 1 mcfbN^Q5 6.02x10 N 20 5molecules , „ 21
1.OS^f-N^C^x ——— x = 6.02x10 N20 5molecules
^ lO S T g - N ^ lrn o F N ^ C b

E X E R C IS E 2 . 2 7 How many molecules are there in 5.6 L CO2 at STP ? 1.5x102 3

EXAM PLE 2 .3 0 U n d ersta n d ing M ole C oncept

P r o b l e m ." Answer the following questions for P 2O 5 that contains 0.62 g of phosphorus. (P = 31, О = 16)
(a) Find the mole number of P 2O 5 (b) Find the number of molecules of P 2O 5
(c) Find the mass o f О in the compound (d) Find the total number of atoms in the compound
S o lu tio n :
(a) 0.62 g P -» ? mol P -> ? mol P20 5 =» 0,62 Г Р-х 1 пГо№ x l ™ ?I -2.9 .? = Q.Ql mol P 2O s
' 31>R 2 mDH>
23
(b) 0.01 mol P 20 5 -> ? molecules => 0.01 п тоЬ ^Х )5x 6 -02 x 10 p 2°5 _ 6 Q2 x 1()21 moiecuies
1-тоТЕз_ 0 5

(c) 0.01 mol P 2O 5 -» ? mol О ? g О => 0.01 m o H y O s x - x 16 g 0 = 0 .8 g О

1 incrt-F^Os Гт©1 О

(d) 0.01 mol P 2O 5 —> ? mol (P+O atom) —> ? atom =>
23
0.01 irrnl-P-4.D cX 7 11101 а1<)" ' X 6iL2xl ° atoms = 4 2 x 1022atoms
l'm n l-P ^ D 5 " Т т г т Ц й о т

2.7 ATOMIC W EIGHT DETERMINATION

—
E X A M P L E 2.31 F in d in g A to m ic W e ig h t
Problem : 0.02 mol Y 2O 5 weighs 2.16 g. Calculate
(a)the molecular weight of the compound. (b) the atomic weight o f the element, Y,
(c)the weight of a single Y atom . ( 0 = 1 6 )
Solution : (a) Molecular weight = the weight o f 1 mol of compound.
0.02 mol Y20 5 2.16 g l
1 mol Y 20 5 д: j * = 108 g or Y20 5 = 108 g/mol

(b) Let Y represent the atomic weight of the element Y Y 2O 5 = 108 => 2 Y +5x16=108 => Y = 14 g/mol
50 Chapter 2

(с) Atomic weight = the weight of 6.0 2 x l0 23 atoms

14 g Y contain 6.0 2xl0 23 Y atoms | x _ 14 - 2 3 x 1 0 23‘T
x к Y 1 Y atom J m 23
r6.02x10

E X E R C IS E 2.28 0 05 m ol Х (С Ю 3) 2 is 15.2 g. Find the atom ic w eight and the w eight o f a single X
atom ? (C l = 35.5, О = 16) i37g/mol, 2.3x1 o ' 2~ g
■' - — .................. — -— — ................

.
E X A M P L E 2.32 F in d in g A tom ic W eigh t
Problem : 3.42 g X 2( S 0 4)3 contains 0.12 mol o f oxygen atom s. W h at is the atom ic w eig h t o f X ? (S = 32)
Solution : T he solution chart o f the problem may be as follows:
0.12 mol О Л ? mol X 2( S 0 4)3 Д MW of X 2( S 0 4)3 Щ AW of X

Step 1 : 12 mol О are present in 1 mol X 2( S 0 4)3

0.12 mol О______________x___________ j jc = 0.01 mol X2(S 0 4)3

Step II : 00.01
.0 1 mol X 22( SSU0 44)3
m ol X ) 3 3.42
3 .4 2 g V
1 mol X 2( S 0 4)3 MW ) MW = 342j

Step I I I : X 2( S 0 4)3 = 342 => 2X + 3x32+12x16 = 342 => X = 27 g/mol

Or, the steps I, and II may be combined as follows.

The formula, X 2( S 0 4)3 shows that 1 mol of X 2(S 0 4)3 contains 12 moles of O, so the mass of X 2( S 0 4)3 con­
taining 12 mol o f О is the molar mass of the compound or the molecular weight of the compound.
0.12 mol О is present in 3.42 g 1
12 mol O MIWW= -?' J' MW = 342 g/mol
The atomic weight may be found as the way described in step III.

EXER C ISE 2.29 104.8 g o f Mg3( Y 0 4)2 contains 0.8 mol of Y. W hat is the atomic weight of Y ?
(Mg = 24, О = 16) M g/m ol

EX E R C IS E 2.30 35.7 g of Cr 2(X 20 4) 3.6H20 contains 8.1 g H20 . What is the atomic weight of X?
(Cr = 52) l2g/mol

E X A M P LE 2.33 F in d in g A to m ic W e ig h t, U sin g M o le R e la tio n s

Problem : 10.4 g of X combine with oxygen to form 15.2 g of X 20 3 . W hat is the atomic weight of X ?
1б? I II III IV v
Solution ; Data -» mass of О -+ mol of О -> mol of X 20 3 4 MW of X 20 3 AW o f X

Step I. : m0 = т х ,сь - mx = 15.2 - 10.4 = 4.8 g Step II. : n D = - ...g = 0.3 mol О
16 g/mol
1 mol X 2 0 3 s m n IV ■ „ - m m w - m - 1 5 -2 8 -
StcP Ш- 0.3 mol О x l m 0l. X2.U ‘ = 0.1 mol X 2 0 3 SteP IV - : 11 = MW = ” = = 152 # « 1
3 mol О
Step V. : X 20 3 = 152 =* 2X + 3 x 16 = 152 => X = 52 g/mol

O r the steps II, III, IV may be combined as follows : From the formula we see that one mole X 20 3 contains
 A Scientific Model : Atomic Theory 51

3x16=48 g O. Then the mass of compound containing 48 g of О is its molecular weight.

If 4.8 g О is present in 15.2 g X 2O 3 1
48 g 0 MW } MW = 1 5 2 g/mol

EXERCISE 2 .3 1 When 1.92 g Y is healed with aluminum, 3 g of AI2Y 3 isformed. W hat is the atomic
weight of Y ? (Ai = 27) 32 g/mol

EXAMPLE 2 .3 4 F inding A tom ic W eight by Using M ole C oncept

Problem : If 70 % of x 20 3 is X by weight, what is the atomic weight of X ? 0=16
Solution : If 70 % o f X 20 3 is X, then 30 % of X 20 3 is oxygen.
In the compound 2 mol o f X combine with 3 mol of O. The weight o f 3 mol of О = 3 x 16 = 48 g
In that case 30 % of X20 3 is 48 g. Then 100 % of X 20 3 will be the molecular weight of X 20 3 :

If 30 % of X 20 3 weighs 48 g
100 % o f X20 3 weighs MW }
J MW = 160 g/mol

x 20 3 = 160 g/mol => 2xX+3x16 = 160 => X = 56 g/mol

EXERCISE 2 . 3 2 П 4 3 « of X(OH): is oxygen by weight what is the molecular weight of the compound?
( 0=16, H = 1 ) 74.4 g/mol

EXERCISE 2 . 3 3 The compound, X tY iO 7, is 26.57 ‘3 X and 35.36 % Y by mass. W hat arc the atomic
weights ol X and Y ? (O = 1 6 ) ' 39 g/mol, 52 g/mol

E X A M P LE 2 . 3 5 F in din g M o lec u la r W eight

Problem : 0.25 mol of CnH2n2 contains 1.5 mol of H atoms. What is the molecular weight o f the com ­
pound ? (C = 12 ; H = 1)
Solution : If 0.25 mol contains 1.5 mol of H l гтт /
1 mol x }
f x = 6 mol of H

/
Now we can calculate the value ol n from the subscript ol H. 2n - 2 = 6 =? 2n = 8 => n= 4

The formula of the compound is C„H^n 2 or С 4НЛand the MW o f the compound is. (4\ 13) + (6x1) = 54 g/mol.
’ , - ■■■—

EXER C ISE 2.34 0.5 mol compound with a general formula o f С пН з п+2 contains 3 mol o f H.Find the
m olecular w eight o f the com pound (C = 12, H = 1) 30glmol

EXERCISE 2 . 3 5 0.05 mol of X„H;„ weighs 3.5 grams. 85.7 ck of the compound is X by mass. Find
the numerical value of 11 and the atomic weight of X ? •- 5, 12 g/mol

E XA M PLE 2.36 C a lc u la tin g A to m ic W eig h t F rom M o la r V o lu m e

Problem : A 42.6 g of NX 3 (g) occupies 13.44 L at STP : Find the atomic weight of X. (N = 14)
„ , . I и in
Solution : 13.44 L NX 3 at STP -> ? mol NX 3 -» MW of NX 3 -» AW of X
52 Chapter 2

L 13.44 L N X 3x 1 11101 = 0.6 mol N X 3 II. MW = — = 42 -6 ,g .,. - 7 i g/m Qi

22.4 L N X 3 n 0.6 mol
III. NX 3 = 71 g/mol => 14 + 3X = 71 => X = 19 g/mol

EXER C ISE 2.36 9.5 g sample of X 20 3 gas has a volume of 2.8 L at STP. What is the atomic weight
Of X ? 14 g /mol

E X ER C ISE 2.37 The density of X 4H 8 (g) is 2.5 g/L at STP. W hat is the atomic weight of X ?
12 g/mol

EXER C ISE 2.38 Find the atomic weight of X in each of the following problems.
(a) The weight of a single X atom is 1.5 x 10~23 g.
(b) 2.4 x 1023 molecules o f XC12 is 44.4 g (Cl = 35.5)
(c) 5.6 L of XH 3 at STP is 8.5 g (H = 1)
(d) 0.4 mol PX 3 and 0.6 mol PX 5 weigh 367 g. (P = 31)
(e) 3.84 g Li2SiX 6.2H20 contains 0.72 g H20 . (Li = 7, Si = 28)
(a)9glmol (b)40 g/mol ( c ) 3 1g / m o l (d)80g/mol (e)19 g/mol

E X A M P L E 2 . 3 7 D e te r m in in g A to m ic W e ig h t F r o m G r a p h ic a l A n a ly s is .
Problem: The graph given aside shows how the
masses of XY and X2Ys compounds vary with respect
to the mol number of X element in the compound. Use
the graph to find the atomic weights o f X and Y ele­
ments.

Solution : From the graph it is shown that 0.2 mol

o f X is present in 6 g XY and in 10.8 g of X 2Ys. Using
m ass o f c o m p o u n d (g) this data we can find the atomic weights of X and Y as
follows.

I П
0.2 mol X ? mol XY -> molecular weight of XY

0.2 mol X x 1 mol XY = 0.2 m ol XY, MW = — = - — = 30 g/mol XY = 30 g/mol

1 mol X ' n 0.2 mol

0.2 mol X —> ? mol X2Ys -+ molecular weight of X 2Ys

0.2 mol X x — = 0.1 mol X 2Y 5, MW = - = i M i _ = Ю8 g/mol =* X 2Y 5= 108 g/mol

2 m o lX n 0.1 mol
So, XY = 30 g/mol X + Y = 30
X 2Y 5 = 108 g/m ol ) 2X + 5Y = 108

Multiplying the first equation by (-2) gives - 2 K - 2 Y = -6 0

4. Ж & 5Y = 108
3Y = 48 => Y = 16 g/mol
and the atomic weight of X is : X + Y = 30 => X = 30 - 16 = 14 => X = 14 g/mol
 A Scientific M o d e l: Atomic Theory 53

EXERC ISE 2.3S

С The graph given aside represents the relationship between mass of
/ compound, C 4 H 7 ( O H ) x and the mol number of С it contains.
4 ^ °-3
оt в
3
Using the information in the graph find the numerical value of x.
-С о
с 3
g 1 0.1
м о
о о
ЕS
2.65 7.95
m ass o f со m pound (g)

EXER C ISE 2.40 50 g Х 2(У 0 4 )з contains 0.25 mol X, and the compound is 24 % Y by mass. Calculate
the atomic weights of X and Y. 5 6 g / mo l , 3 2 g / m o l
.-.....UU..............

2.8 P E R C E N T A G E C O M P O S IT IO N OF C O M P O U N D S

The percentage by w eight o f elem ent in a com pound is the sam e as the
number o f grams o f that elem ent present in 100 grams o f the com pound. The
percentage com position o f a compound is easily calculated from the formula o f
the com pound.
The subscripts o f the formula give the number o f m oles o f each elem ent
in a m ole o f the com pound .The percentage o f a given elem ent is 100 tim es
the m ass o f the elem ent divided by the mass o f a m ole o f the com pound.

% e le m e n t - m a s s o f e le m e n t in t h e co m p o u n d ^ lQQ
m o le c u la r w e i g h t o f t h e c o m p o u n d

EXA M P LE 2.38 C a lc u la tin g P e r c e n ta g e o f an E le m e n t in a C o m p o u n d

Problem: W hat is the percentage by mass o f each element in Al2 (S 0 4)3 ?
Solution: MW of Al2 (S 0 4)3 = 2 x 27 + 3 x 32 + 12 x 16 = 342 g/mol

% A1 = ------- — mass of A1 — _ _ x 1()0 ^ % A1 = _54_ x 1()() _ 15 8 %

molecular weight of A l^ S O ^ 342

similarly % S = — x 100 = 28.1 % and % О = — x 100 = 56.1 %

342 342

A check show s that the sum o f the percentages of the elem ents in the com pound is equal to 100 c/<.

EXERCISE 2.41 W hat arc the percentages o f boron, and w ater in borax, N a 2 B 40<; (O H ^ .X fb O ?
(Na = 23, В = 1 1 , 0 = 16, H = 1) 11. 5 % H, .17.7 % H 2()

EXERCISE 2.42 W hich o f these fertilizers has the highest percentage hv m ass o f nitrogen 1
(a) Urea, N 2 H ^ C '0 (b ) A m m onium nitrate, N H 4N O 3 (c) A m m onium phosphate (N H .J V 5P O 4

E X A M P LE 2.39 C a lc u la tin g P e r c e n ta g e C o m p o sitio n F r o m M a ss D ata

Problem : A sample of a compound contains 18.02 g C, 2.52 g H, 3.50 g N, 4.00 g О and 8.02 g S. What
is the percentage by mass of each element in the compound ?
54 Chapter 2
Solution: The weight of the sample = 18.02 + 2.52 + 3.50 + 4.00 + 8.02 = 36.06 g
% of С = -°-2- x 100 = 49.97 % of H = — x 100 = 6.99 % of N = - M L x 100 = 9.71
36.06 36.06 36.06
% of О = x 100 = 11.09 % of S = x 100 = 22.24
36.06 36.06

E x e r c i s e 2.43 A sam ple having a m ass o f 0.924 g w as decom posed into its co m ponents and found to
have 0.389 g o f carbon, 0.059 g o f H and 0.476 g o f O. Find the percentage com position o f this substance '?
C:-I2.l%, 4:6.4% . 0:51.5%

2 .9 D E R IV A T IO N O F E M P IR IC A L FO RM ULAS
A s explained before, the em pirical fo rm u la specifies the relative n u m b er
o f ato m s o f d iffe re n t kind in the co m pound. T h e an aly sis g iv es th e p ro p o r­
tions by m ass o f th e elem ents that m ake up the com pound.

T h e r u le s fo r d e r iv in g an e m p ir ic a l fo r m u la :

1. T h e p erc e n tag e c o m p o sitio n o f the co m p o u n d is d eterm in ed e x p eri­

m entally. If the data arc given in term s o f the n u m b er o f gram s o f each elem ent
in a sam ple, there is no need to find the percentages.
2. The num ber o f grams o f each elem ent is converted to the num ber o f
moles o f atoms o f each e le m e n t . R em em ber n = m
AW
3. Each value obtained in step 2 is divied by the sm allest value. If the d i­
v isio n b y the sm allest valu e produces a ratio th at still has decim als, m ultiply
each n u m b e r by the sm allest fa c to r th at co n v erts all the term s to in teg ers in a
such w ay that w hole num bers w ill result.
4. A ratio by moles o f atom s is the sam e as a ratio by atoms. The whole
numbers obtained in step 3 are the subscripts o f the empirical form ula.

E X A M PLE 2.40 F in d in g E m p ir ic a l F o r m u la F ro m M o le C o m p o sitio n

Problem: A compound consisting of only С and H is found to contain 0.5 mol of С and 1.25 mol of H.
W hat is the empirical formula of the compound ?
Solution: The subscripts in the formula shows the number o f moles of elements. The formula of a com ­
pound made from x mol of the element A, and у mol of the clement В may be written as A^B^. In this formula x
and у must be integer numbers.
Keeping this reasoning in mind we may write the formula of the compound as C 0.5H 1.25- This formula cannot
be the empirical formula because the subscripts are not integers. To change them into integers let us divide the
subscripts by the smallest integer, 0.5. ,, u
k £ k ^ = , C lH 25
05 0.5 1 ^

But this division still produces a decimal number 2.5. To change this into the sm allest integer number let us
multiply all the subscripts by the smallest factor that converts 2.5 to an integer, which is 2.

(C iH 2.5)2 => C 2H 5 (The empirical formula)

In some cases, because of the experimental errors, the result of an analysis may not produce exact integers for the
subscripts. In this case we have to convert them to the closest integers.
 A Scientific Model : Atomic Theory 55

E X A M P L E 2.41 C a lcu latin g Em pirical Form ula Fro m M ass C om p osition

Problem : W hat is the empiricalformula of a compound consisting of 7.8 g of K, 7.1 g o f Cl and 9.6 g of
О? К = 39, Cl = 35.5, О = 16 m
Solution : Step I : Convert the grams into moles. Remember n =

n K= 7 '8 g = 0 .2 mol К na = — l A f - 0.2 mol Cl n Q= 9 '6 g = 0 .6 mol О

39 g/m ol 35.5 g/mol 16 g/mol

Step I I : W rite the crude formula using the mole numbers as subscripts, and divide them by the smallest sub­
script, 0.2.
K 0.2C I 0.2P 0.6 => КСЮ 3
Since the subscripts are the smallest integers, it is the empirical formula of the compound.

EXERCISE 2.44 When 10.24 g ol Cu is healed in an atmosphere of oxygen 11.52 g of an oxide of cop­
per is produced. What is the empirical formula of the oxide formed ? Cu = 64, О = 16 CuyO

E X A M P LE 2.42 C alculating a M olecular Form ula from Em pirical Form ula

Problem : A 2.522 g sample of pure caffeine contains 1.248 g of carbon, 0.130 g of hydrogen, 0.728 g of
nitrogen and 0.416 g of oxygen. W hat is the simplest formula of caffeine? If the molecular weight of caffeine is
194, what is its molecular formula ?
Solution : We will calculate the mole number of each element in the sample
n c - .l -248 = 0 .1 0 4 m ol, n„= = 0.130 m ol, n N= = 0.052 m ol, n 0 = ^ ^ - = 0.026 mol
12 1 14 16

C 0. 104H 0. 130N 0.052O 0.026 and dividing all the subscripts by the smallest one, 0.026, gives C 4 H5N 2O

To find the molecular formula let us compare the empirical formula mass and molecular formula mass (or MW),
the empirical formula mass : C 4H 5N 2O = 4x12+5x1+2x14+1x16 = 97g/mol
the molecular formula mass or MW = 194 g/mol
the ratio of MW to the weight of empirical formula is 194/97 = 2. Then we shall say that the number of atoms
in the molecular formula is twice those of in the empirical formula. Or the molecular formula is :
(C 4H 50 2N )2 CSH 10O 4N2.
Or generally : (Empirical formula) x n = molecular formula,
n is an integer that equates the weight of the empirical formula to the molecular weight.

E X A M P L E 2 . 4 3 D e te r m in in g E m p ir ic a l (S im p le s t) F o r m u la
Problem ; W hat is the simplest formula of the compound that shows the following analysis, 44.83 % potas­
sium, 18.39 % sulfur, 36.78 % oxygen ? К = 39, S = 32, О = 16
Solution : For sim plicity we may assume that we have 100 g of compound. The mass of each element is
then 44.83 g of K, 18.39 g of S, and 36.78 g of O. Now follow the usual procedure described in the previous ex-
amples. n R _ 44.83 g = , 15 nu)| n s = 18,39 g = 0 .5 7 5 mol n 0 = 36-78 g = 2.30 mol
39 g/mol 32 g/mol • 16 g/mol
The empirical formula is K4 4 5S 0 575O 2 30 => K 2SO.}

EXERCISE 2.45 A com pound has the follow ing percentage com position by m ass. 58.8 c/< C. 9.8 % II.
and the rem ainder is oxygen, (a) C alculate the em pirical formula o f the com pound. (b) II 0.2 mol o f the com
pound w eighs 40.8 g, find its m olecular form ula. (a) < 5 / / щОу (b) С щ П y<i(>j
56 Chapter 2

E X E R C ISE 2 . 4 6 Cocaine is 67.30 % C, 6.98 % H, 21.10 % O. and 4.62 % N. What is the sim plest
formula of cocaine ? С ц Н 2 1 O 4N

EXAM PLE 2 . 4 4 D eterm inin g Empirical Form ula

Problem ; A given compound consists of 6.02 x 1022 atoms of carbon, 1.806 x 1023 atoms of hydrogen and
6.02 x 1022 atoms o f oxygen. W hat is its simplest formula ?
Solution ; For the simplest formula, we need to know the relative numbers o f atoms. As the basis of refer­
ence, it is usually m ost efficient to consider the smallest number, that is 6.02 x 1022 atoms of carbon.
22 23 .
6 .0 2 x 1 0 atom s of С , , m ™ 1 .8 0 6 x 1 0 atoms of H , itn m rA fu n
= 1 atom 01 С per atom С = 3 atoms ol H per atom С
6 .0 2 x 1 0 atoms of С 6 .0 2 x 1 0 atoms of С
22

_x aloms »1 ° = 1 atom of О per atom С Then, the sim plest formula is С H f)

6.02 v 10 atoms of С

E X E R C I S E 2 . 4 7 T he analysis of a compound showed that it was made up 7.2 g C, 1.2 mol o f H, and
3.6 x 10- atoms of oxygen. What is the molecular formula of the compound if its molecular weight is 180
g/mol ? С = 12, О = 16, H = I C(>H n( ) (
 A Scientific Model : Atomic Theory 57

S O M E N EW TE R M S

Anion is a negative ion that is formed when a Metalloid is an element that has both metallic
neutral atom gains an electron. and nonmetallic properties.
Atom is the sm allest particle of m atter that M ix t u r e is any m atter consisting of two or
characterizes an clement. more substances physically combined in no particular
Atomic mass unit (amu) is a basic unit for proportion by mass.
expressing the masses of individual atoms. One amu Molar volumes to the volume occupied by 1
is 1/12 of the mass of a carbon -12 atom or 1 amu = mole of substance.
1.6606x 10-24 g. M ole is the am ount of a chemical substance
Atomic weight is the relative mass of an cle- that contains Avogadro's number (6.02 x 1023) of for­
- ment’s atom that contains Avogadro's number of actu­ mula units.
al atoms. Molar volume is the volum e occupied by 1
mole of substance
A vogadro's num ber is the num ber of ele­
M olecular form ula is a chem ical form ula
mentary unit in one mole and has a value of 6.022 x
that identifies the actual composition of one molecule.
1023.
M olecular weight (also form ula weight)
Binary compound is a compound composed is the sum o f the atomic weights of all the atoms
of two different elements. present in the formula of a compound.
Cation is a positive ion that is formed when a N om enclature is a systematic way of writing
neutral atom loses arrelectron. the chemical names and formulas of compounds.
Compound is a substance formed from two or N onm etals are elem ents whose atoms tend to
more different elements always combined in a fixed ra­ gain electron(s) to form anions.
tio. Oxidation number is the charge on an atom
in a compound.
Element is the sim plest substance that cannot
Polyatomic ion is an ion composed of two or
be decomposed into components by any means.
more atoms.
Empirical (Simplest) formula is a chem i­ Pure substance is a substance (elem ent or
cal formula that indicates the ratios of numbers of at­ compound) that has characteristic properties that identi­
oms of the elements present in a compound.
fy i t .
Emulsion is a colloidal dispersion of a liquid Solution is a homogeneous mixture.
in another. STP stands for standard temperature and pressure
F o r m u la is a shorthand way of w riting the (°C and 1 atm)
names of compounds using chemical symbols. Structural formula is a chem ical form ula
that indicates how atoms are connected to each other
Heterogeneous mixture is one that has two
and how they are arranged in space..
or more phases with different properties.
Suspension is a hom ogeneous m ixture in
Homogeneous mixture is a mixture that has
which the particles of one (or more) substances are dis­
uniform properties throughout.
persed uniformly.
Metals arc elements whose atoms have tenden­ Ternary compound is one that is made up of
cy to lose electron(s). three different elements.
I

V ■ ! :' -

V
58 Chapter 2
REVIEW QUESTIONS
2.1 Classify each of the following as an element, g) Ammonium chromate h) Potassium phosphate
compound or mixture. Justify each answer. l) Nickel (II) chlorate j) Copper (I) bromide
a) mercury t \ d) pure water *3- g) pure ice С k) Zinc phosphate 1) Chromium (III) sulfate
b) milk e) ink c r \ h) carbon £ m) Potassium permanganate n) Tin (IV) oxide
c) air гл f) salty water t) brass H 0) Aluminum hydroxide p) Lead (II) acetate
b)llaS g)(NH4)2 C r 0 4 n)Sn02 p)Pb(CH3C О О ) 2
2.2 Suggest a method to separate the components of
the following mixtures made up of 2.7 W rite the chemical formula of each of the follow­
a) olive oil and water b) alcohol and water ing compounds.
c) copper dust and table salt d) sugar and water a) dinitrogen tetroxide b) Sulfur hexafluoride
c) tetraphosphorus decoxide d) Bromine trifluoride
2.3 How many atoms are present in each of the fol­ e) Sulfur dioxide f) Phosphorus pentachloride
lowing molecules ? г г •?' b ) S F ,5 c ) P 4 O 7 0 f)PCl5
a) C a(O H )f: 1 4 b) N a 2S 0 4 c) A12( S 0 4)3 Give the names of the following compounds,
d) N a 2H P 0 4 e) K 3[Fe(CN)6] 0 CH 3COC 2H 5 a) KC1 b) KC10 3 c) FcO d) Fe 20 3
g) K 2B 40 7 .5H 20 h) Ce(NH 4) 2(N 0 3)6 e) N a2S I) C u S 0 4 g) K 2Cr 20 7 h) NH 4N 0 3
1) N al j) Mg 3( P 0 4)2 k) S2C12 1) CrCl 3
2.4 The structural formula for glucose is m) S 0 3 n) B aC r0 4 o) SnBr 4 p) C120 7
H H H H H H r) P 40 6 s) N 20 3 l) SC16 u) CuBr 2
i i i i t i v) M g S 0 4.7H20 y) C aS 0 4.2H20
H - C - C - C - C - C - C = 0
o)Tin(IV)bromide r)Tetraphosphorus hexox-
OH OH OH OH OH
ide u)M agnesiumsulfate heptahydrate
W hat are the molecular and empirical formulas of glu­
cose ?
( ^ D e f i n e the following terms
2.5 W hat are the similarities and differences between a) element b) compound c) ion
the simplest fonnula and molecular formula of a com­ d) cation e) anion I) metal
g) hydrate h) binary compound 1) ternary compound
pound ?

2.10 Define the following terms

( i j ) W rite the chemical formulas for the following
a) amu b) mole
compounds
a) Sodium oxide b) Barium sulfide c) atomic weight d) molecular weight
c) Magnesium nitrate d) Silver nitrate e) molar volume f) Avogadro's Hypothesis
e) Calcium carbonate f) Iron (III) chloride g) the actual mass of an individual atom

REVIEW PROBLEMS
2.11 Calculate the molecular weight of each of the c) 4 .8 x l0 24 0 2 molecules d) 72 g Mg
following compounds* e) 93 g P 4 0 15.2 g N 20 3
a) C a C 0 3 b) (NH 4) 2S 0 4 c) Mg 3( P 0 4)2 g) 2.2 g C 0 2 h) 28.4 g P 20 5
d ) C 3H 5(OH )3 e) M g S 0 4.7H20 f) Fe 4[Fe(CN )6]3 1) 5.6 L C 0 2 at STP . j) 134.4 L H 2 at STP
g) C 55H 72MgN 40 5(chlorophyl) a)0.02 d)3 e ) Q. 7 5 f)0.2 i)0.25
b)132 f)860 g)892 2.13 Calculate the num ber of atoms in each of the
2.12 Determine the number of moles in each o f the following
following : a) 2.5 mol Mg b) 0.2 mol P 4
a) 1.2xl0 22 A1 atoms b) 1.8xl0 23 Zn atoms c) 96 g S 8 d) 8.96 L 0 3 (g) at STP.
a ) 1 . 5 x 1 0 24 b)4.8xJ023 d)7.2x!02 3
* H : l , H e:4 , C :12, N :1 4 , 0 :1 6 , N a :2 3 , M g :2 4 , A l:2 7 , P:31, C a:40, Fe:56, P b:20 7
 A Scientific Model '.Atomic Theory 59

2.14 C alculate the num ber o f molecules in each of C 4H 10, at STP. (C = 12, H = 1) Find
the following t a) its mole number b) its molecule number
a) 4 mol CH 4 b) 12.8 g S 0 2 c) the mole number of С atoms it contains
c) 27 g H 20 \ d) 11.2 L C 0 2 at STP d) the mole number of H atoms it contains
b ) 1 .2 x l0 23 d)3.01xl0 2 3 e) the total number of atoms it contains
2.15 Calculate the mass, in grams, of each of the fol­ 1) its volume
lowing. c)2mol e )4 .2 x l0 24 f)11.2 L
a) 6 mol H 2S 0 4 b) 0.2 mol N a 2C 0 3 2.21 Answer these questions for N 20 3, gas at STP,
c) Avogadro's number of H2S molecules that contains 3 moles of N atoms. Find (N=14, 0= 16)
d) 9.0 3 x l0 23 C i 2H 220 n molecules a) The mole number of N 20 3
e) 2.24 L S 0 3 at STP f) 5.6 L N 20 3 at STP b) The mass of N 20 3
b)21.2 c)34 f)1 9 c) The mass of О atoms it contains
2.16 An average signiture written in pencil contains d) The volume of the gas at STP
about 1 mg of carbon. How many carbon atoms are a)1.5mol c)72 g d)33.6 L
used in an average signiture? 5.02x10 19 2.22 Find the number of moles in each of the follow­
ing compounds containing 0.06 mol of О atom
2.17 Arrange the follow ing in order of increasing a) S 0 2 b) H 2S 0 4 c) A12( S 0 4)3
mass d) C 0 2 e) C a S 0 4.2H20
a) 0.001 mol H20 molecules b) 1000 atoms of leafr a)0.03 b)0.015 c)0.005 d)0.03
c) 2.24 mL of 0 2 at STP d) 6 .0 2 x l0 21 He atoms 2.23 Calculate the mass of each o f the following
compounds that contains 0.25 mol of С atom,
2.18 The density of aluminum is 2.7 g/cm 3. Calcu­ a) C a C 0 3 b ) C 6H 120 6 c) C 4H 10 d) CH3COOH
late a) The number of aluminum atoms in an alum i­ a)25 g b)7.5 g c)3.63 g d)7.5 g
num cube with an edge length of 2 cm. b) The molar 2.24 Find the mass of each of the follow ing com ­
23 3
volume of aluminum. a )4 .8 x l0 b)10cm pounds that contains Ayogadro's number of atoms to­
tally
2.19 Answer these questions for silver, Ag. a) CO b) H20 c) Mg 3(P 0 4)2 d) C u S 0 4.5H20
(Ag = 108, d = 10.5 g/cm3) Calculate / a) l d g b) 6 g c)20.2 g d)11.9 g
a) the number of mol of Ag atoms in 4.32 ^ 2.25 Determine each of the following
b) the mass of 1.2xl0 23 Ag atoms a) moles of oxygen atom in 6.2 g calcium phosphate
c) the volume of 0.4 mol of Ag b) number of hydrogen atoms in 33 g of ammonium
d) the number of atoms in a Ag sample of 20 cm 3 vol^» sulfate
ume c) the volume, at STP, of carbon dioxide that contains
e) the mass and volume of an individual Ag atom. 12.8 g of oxygen
a)0.04 b)21 . 6 c)4.1cm 3 d )1 .2 x l0 2 4 d) grams of sodium atom in 57.2 g sodium carbonate
e) 1 . 8 x l O' 22 g , 1.7 x l О' 23 с m 3 deqahydrate
2.20 A nsw er these questions for 29 g butane gas, a)0.16 b)1.2xl024 c)8.96L d)9.2g
'
M ixture P ro b lem s
2.26 How many oxygen atoms are present in a mix­ 2.28 A 0.4 mol mixture of NO and N 0 2 gas weighs
ture composed of 0.4 mol N 20 3, 16 g S 0 3, and 5.6 L 16.8 g. W hat is the percentage by mol of NO in the
o f C 0 2 at STP ? l .4 x l 0 24 mixture 25%

2.27 The mass of a mixture containing equal number 2.29 A 8.96 L mixture of CO and C 0 2 gases at STP
Of C 3Hg and S 0 3 molecules is 6.2 g. W hat is the is 16 g. Calculate the mass of CO in the mixture?
mass o f S 0 3 in the mixture ? 4g 2 .8 g

C = 12, S =32, N a = 2 3 , N = 1 4 , P b=207, H e = 4 , A l= 2 7 , C a=40, M g = 2 4 . P =31

 60 Chapter 2

*2.30 A sam ple com posed of a m ixture of CH 4 *2.32 A 10 g mixture of C 2FI6 and C 3H 4 gases con­
molecules and C 2H5 molecules analyzes to show 22 % tains 1.6 mol of hydrogen atoms. Calculate the mass
by weight of hydrogen. W hat is the ratio of CH 4 to percentage o f C 2H 6 in the mixture ? 60 %

С гН 6 molecules in the mixture ? 5/4

*2.33 A given mixture consisting only o f Na 2SC>4
*2.31 A 62 g mixture of methane, CH 4, and ethane, and K 2SO 4 analyzes to show 63 % SO 4 ' by weight.
C 2H 6 gases contains 48 grams of carbon. W hat is the W hat is the ratio by w eight of Na 2S 0 4 to K 2SO 4 in
mass o f CH 4 in the mixture ? 32 g the mixture ? 1.7

P e rc e n ta g e P ro b lem s
2.34 Calculate the percentage composition by mass 2.38 W hat weight of mercury is found in 1 ton of an
of the compound. ore which is 35 % cinnabar, HgS ? 3 0 1 .7 k g .

a) AI2S 3 b) Fe 20 3 c) NH 4N 0 3 d) C u S 0 4.5H20 2.39 The most important ore of chromium contains

a )36% A 1,64%S d )2 5 .6 % C u ,1 2 .8 % S ,5 7 .6 % ()
chromite, F eC ^C V Calculate the weight of chromium
in 10.0 tons of ore which contains 5.0 % chromite.
2.35 The m ineral turquoise has the formula 2 3 2 .1 kg
СиА 1б(Р 0 4)4(0 Н)§.4 Н 2 0 . Find the percentage of the 2.40 Calculate the percentage of copper in 1 ton of
following in the mineral. a)Cu b)Al c)P d )0 e)H 20 ore containing 5 % malachite, CuC 0 3.Cu( 0 H) 2.2. 9%
a ) 7 .8 6 % b)19.9% e)8.85%
2.36 Given the compound AB3. If the atomic weight **2.41 a) Given three elem ents X, Y, Z. If com ­
of A is twice the atomic w eight o f B, calculate the pound XY 2 is 72.72 % by weight X and compound
mass percentage o f A and В in the compound. Z 2X is 88.88 % by weight X, what is the percent by
40%A, 60%B
weight of X in the compound Y 3Z 6X ? 5 7 .1 3
2.37 0.1 mol of a com pound of С and H elements b) Given three elements X, Y, Z. If compound XY 2 is
contains 0.3 mol of С and 0.4 mol of H. W hat is the 73.7 % by weight Y, and compound YZ 2 is 28.0 % by
percentage composition of the compound by mass? weight Y, what is the percent by weight o f Y in the
90% C ,10% H
com pound X Y 2Z 4 ? 2 5 .4

A tom ic W eig ht and M olecular W e ig h t D eterm ination

2.42 A single X atom is 9.3x10-2 3 g. W hat is the ' 2.47 1.02 g of Y 20 3 contain 0.015 mol of O 2 molc-
J atomic weight o f X ? 5 6 g /m o l cules. W hat is the atomic weight of Y ? 27 g

\ \ 2.43 2.4x10 Z molecules weigh 2.4 g. W hat is the 2.48 M olecular weight of X 3Y 4 is 40 g and 10 % of
weight of 1 mole of Z molecules ? 60 g/mol it by weight is Y. W hat is the atomic weight of X ?

i ЧЬ
2.44 0.05 mol X 2O 3 weighs 5.1 g. C alculate the 2.49 One mole of a compound contains 1 mol o f X
1 2 s

atomic weight of X. (O = 16 g/mol) 2 7 g/mol and 3 mol of Y and its molecular weight is 80 g. If the
atomic weight .of X is twice the atomic weight of Y,
2.45 19.2 g of Х гН ^С О з has 0.4 mol o f X atom. what are the atomic weights of X and Y ?
с Find the atomic weight of X ? 1 4 g /m o l X=32, Y=16
2.50 W hen 44 g o f X 2O are placed in a container
2.46 1.88 grams of X 2O contains 1.56 grams o f X. which has 44 g o f CO 2, the number of molecules be­
C alculate a) the m olecular w eight o f X 2O b) the comes twice the initial number of molecules. What is
atom ic w eight o f X. 9 4 g /m o l, 3 9 g / m o l the atomic weight of X ? 14 g
* M ore challenging problem s are m arked w ith an asterisk

/ '
 A Scientific Model : Atomic Theory 61

J 2.51 A compound with a formula of X 2S 3 is 36 % X formed reacts with Ba to form BaX. If BaX react com ­
by mass. W hat is the atomic weight of X ? pletely with potassium , 82.5 g o f K2X is formed,
27 g /m o l what is the atomic weight of X ? (Mo = 96, К = 39)
2.52 20 g of XO 3 (g) occupies a volume of 5.6 L at 32 g / m o l

STP. Find the atomic weight of X. 3 2 g /m o l **2.58 A bottle contains elem ents X and Y so that
there is one atom of X for every three atoms of Y. The
2.53 6.2 g of the com pound, Хз(УС>4)2 contains total weight of the sample, of which X contributes 20
2.4 g of X and 0.04 mol of Y. Calculate the atomic %, is 120 g. If the atomic weight of X is 24 g, what
weights o f X and Y. 4 0 g /m o l, 31 g / m o l would be the atomic weight of Y ? 3 2 g /m o l

2.54 Given that **2.59 A given mixture composed of 0.01 mol of A

I. 2.8 L of XY 2 (g) at STP is 8 grams. and 0.02 mol of В weighs 0.76 g., Another mixture
II. 6.0 2 x l0 21 Z 2 X Y 4 molecules weigh 0.98 grams. composed of 0.04 mol of A and 0.01 mol of В weighs
III. 0.25 mol of Z 2X is 8.5 grams. 0.8 g. W hat is the weight of 1 mol of A ? 12 g/mol
Compute the atomic weights of X, Y and Z elements.
32 g/mol, 16 g/mol, 1 g/m ol **2.60 2.5 g of X, 0.02 mol of Y, and 1 .2xl0 23 Z
*2.55 A 33.2 g sample o f Ag 2XC>4 is converted to atoms are reacted and 5.3 g o f X 3Y Z 6 are formed at
the oxidfTX 20 3 , yielding 7.6 g. W hat is the atomic most. Find the atomic weight of Z ? (X = 25, Y = 70)
weight of X 7 (Ag = 108, 0 = 1 6 ) 52g/mol 20 g/m ol
2.61 The weights of 1 mol of each of XY2, and Х2Уз
*2.56 The metal M form s the sulfate M ^ S C ^ ^ A are 46 g and 76 g respectively, what is the weight of
sample of-this sulfate weighing 0.684 g is converted 0.02 mol of X 2Y 5 ? • 2 .1 6 g

to 1.398 g BaSC>4. W hat is the atomic weight of M ?

2.62 2.86 g of Na 2C 0 3 .xH 20 is dissolved in enough
(Ba = 137, S = 32, О = 16) 27g/mol
water to make 200 mL o f solution. If 6 .0 2 x l0 19 Na+
ions tire present in 1 mL of solution, what will be the
**2.57 48 g o f molybdenum (Mo) reacts completely
value of X in the formula ? N a = 23, С = 12, О = 16,
with the elem ent X to form Мо 2Х з. All of М о2Хз
H= 1 ю

D eterm ining Em pirical and M o lec u la r F o rm ulas

2.63 The elem ental analysis o f several compounds 2.66 W hat are the em pirical form ulas o f tlte com ­
are given below. Determine the empirical formula of pounds with the following compositions
each compound whose composition to be a) 70 % Fe, 30 % О
a) 5.6 g F c and 2.4 g О b) 0.64 g S and 0.64 g О b) 38.71 % C, 16.13 % H, and 45.16 % N
c) 2.82 g К, 2.56 g Cl, 4.62 g О c) 26.53 % K, 35.37 % Cr, remainder is oxygen.
d) 18 g C, 1.65 g H, 2.10 g N and 2.4 g О d) 21.8 % Mg, 27.8 % P, and 50.3 % О
e) 4 g Ca, 6.02 x 1022 С atoms, 0.3 mol О e) 79.1 % C a S 0 4, 20.9 % H20
f) 2.78 g Co, 11.96 g I, and 4.52 g О 1) 37.7 % Na, 22.95 % Si, the remainder is oxygen
a )F e 20 3 с)КСЮ4 e ) C a C ()3 a ) F e 2 G 3 (c)K2 C r 20 7 (e )C a S 0 4 . 2 H 20
- 2 ^ 4 When 3 g of Mg is burned in excess oxygen, it 2.67 A compound with a known molecular weight of
produces 5 g of magnesium oxide. W hat is the empiri­ 28, contains 85.71 % carbon and 14.29 % hydrogen.
cal formula of the oxide formed ? Mg = 24, О = 16 Find its molecular formula. C2H 4
Mg О
2.65 When 5.8 grams of silver oxide are decomposed, 2.68 A sample of a com pound is found to contain
there remains a silver residue of 5.4 grams. Calculate 0.97 grams of phosphorus and 1.25 grams of oxygen.
the simplest formula o f silver oxide ? If 0.02 mot of this compound weighs 5.68 g, calculate
A g 2(> its molecular formula. 1' 4 ° 1 0
02 Chapter 2

2.69 0.02 mol of compound with a general formula there was obtained 14.8 g of Mg(N 03)2 and 23.3 g of
С пН 2п+гО weighs 1.2 g. W hat is the m olecular for­ B aS 0 4 . Calculate the em pirical formula o f the com ­
mula of the compound ? СзН 80 pound. Mg = 24, Ba = 137, S = 32, N = 14
M g 2S 2 ° 7
2.70 The percentage by mass of sulfur in a hydrate of 2.74 A sample of a liquid consisting of only С, H,
copper (II) sulfate is 12.8. W hat is the formula of this and О was analyzed and found to contain 0.6 mol C,
hydrate? CUSO4.SH2O 9.6 x 1023 atoms o f H, and a quantity of oxygen that
has a volume of 4.48 L at,STP. Find
2.71 The ascorbic acid, vitamin C, is found to con­ a) the simplest fonnula o f the compound
tain 40.9 % C, 4.55 % H and 54.55 % O. a) D eter­ b) the mass of compound analyzed
mine its empirical formula b) If 0.05 mol of the com­ c) the molecular formula of the compound if it con­
pound weighs 8.8 g, find its molecular formula. tains 26 atoms per molecule
а)СзН4O3, b)c6H8o 6 a ) C 3 H gO 2 b) 15. 2 g c)C (,H if , О 4
2.72 A sample of tantalium chloride weighing 71.7 g 2.75 A hydrate with a formula of
is treated with AgN 03 giving 143.5 g of silver chlo­ Nia(NH 4)b(SC>4)c.dFl20 was, analyzed. W hen 15.8 g of
ride. Find the empirical formula of the tantalium chlo­ the compound was heated until all the water was driven
ride. Та = 181, Ag = 108, Cl = 35.5 TaCl5 off, 11.48 g of anhydrous compound remained behind.
The composition by mass of the anhydrous compound
*2.73 A compound composed o f only Mg, S, and О was found to be 2.36 g N i2+, 1.44 g N H 4 , and 7.68 g
was analyzed as described below. All the magnesium SO2". W hat is the empirical formula of the compound
atom s was converted to Mg(NC>3)2 and all the S to analyzed ? Ni = 59, N = 14, S = 32
BaSC>4 . From the analysis of 11.2 g of compound N i ( N H 4) 2(S О 4) 2 -6 H 20

SELF TEST
1. The following information is given for a pure sub­ •0.-VVhich is W RONG about NH 3 (g) ? N:14, H :l-
stance. W hicblofothc following proves that the sub­ A) One molecule of compound contains one nitrogen
stance is a compound ? and 3 hydrogen atoms.
A) M elling point is 75°C ; B) 2 mol of this compound is 34 g.
B) Boiling point is 130°C C) The volume of compound containing 2 mol N is
C) Density is 1.5 g/mL 44.8 L at STP.
D) It is slightly soluble in water D) The mass o f com pound containing A vogadro's
E) When it is burned, CCb and H 2O are produced number of H atoms is 17 g.
E) 0.25 mol of compound contains 1 mol of atoms to­
2. Given some form ulas and their names. Which tally.
one (s) of them is WRONG ?
I. ZnCl 2 : Zinc chloride 4. Which one of the following c a n n o t be deduced
II. (NFkrhS : Ammonium sulfate from the formula o f compound ?
III. N 2O 4 : Dinitrogen tetroxide A) Percent composition of the compound.
IV. Cu20 : Copper (II) oxide B) Molecular weight of the compound.
V. Ag 2C 03 : Silver carbonate C) Physical phase of the compound.
VI. РЬ(Ж )з )2 : Lead (IV) nitrate D) The ratio between the weights of the atoms in the
A) I, И, IV, V (6 ), II, IV, VI С) I, V, VI compound.
D) I, III, IV, V V П, IV, V E) The kind of elements in the compound.

I
 A Scientific Model : Atomic Theory 63

i 5.1W hich one contains the largest num ber of m ole­ 1:127)
cules ? (S:32, N:14, C:12, 0 :16) A) F B) Cl С) о D) I Br
A) 1 mol of H2S B) 17 g of NH3
C) 32 g of CH4 D) 0.2 mol of C 0 2 13. If 40 % of X 0 3 is X by weight, which is the m o­
(Ё) 1.204xl025 molecules of CO lecular wcighkpl the compound ?
/ С How many oxygen atoms are there in 0.25 mol of A) 120 B) 80 C) 72 D) 48 ,E) 32
P4O 10 ?
A) 0.25 (®) 2.5 C) 1.5xl024 D) 3.62 E) 2.94 14. 2.7 g of A2B 5 has 3.01xl022 atoms of A. W hich
is the molecular weight 0CA 2B 5 ?
( y . W hich is the mass in grams of K 2C r 207 that con­ A) 27 B) 54 C) 108 D) 135 E) 189
tains 1.12 g of oxygen ? K:39, Cr:52, 0 :1 6
/
A) 2.94 B) 5.88 C) 4.86 D) 3.62 E) 8.82 15. 0.7 mol m ixture o f calcium and m agnesium
weighs 20 g. Which is the mass percentage of Ca in
81 W hat is the mass of a single N 20 3 m olecule ? the mixture ? Ca:40, Mg:24
N :14rO :16 A) 10 B)20 C) 30 D) 40 E) 60
A) 8.82 g B) 6x1 O'23 g C) 1.3xl0"22 g
23
D) 7 .9 x l0 '21 g E) 6xlOZJ g 16. If 0.25 mol of CnH 2nO n is 30 g, what is the val­
ue o f n ? C:12, H :l, 0 :1 6
9. 0.01 mol XBr3 weighs 2.67 g. W hat is the atomic A) I f B) 3 C) 4 D) 5 E) 6
weight of X ? B r : 80
A) 27 B) 19 C) J 2 D) 40 E) 52 17. Upon drying, a 4.92 g of M g S 0 4.xH20 becomes
2.4 g after all the water was driven off. Which is the
10. 16.4 g of C a (X 0 3)2 contain 0.2 mol of X. W hat value of x in the formula ? Mg:24, 0 :1 6 , S:32, H:1
is the atomic weight of X ? Ca:40, 0 :1 6 A) 2 B) 5 C )6 0 )7 E) 10
A) 124 B) 42 C) 32 D>28 E) 14
18. -The density o f X2H 4 (g) at STP is 1.25 g/L.
11. Which is the atomic weight of X ? H:1
m X3 N2 (g) The given graph shows the ( Щ 12 B) 14 C )3 1 D) 40 E) 56
relationship betw een the
50 m ass o f the com pound 19. W hen 8.4 grams of Fe is heated in an atmosphere
X3N2 and the mass of nitro­ of oxygen, 11.6 g of a solid compound is formed.
gen in ihe com pound. Which is the em pirical formula o f the com pound ?
25 / S Fe:56, 0 :1 6
/
/ s
s Which is the atomic weight
/ s m N (g) A) FcO B) Fc20 C) F e 0 3 D) Fe30 4\E ) Fe20 3
of the element X ? N: 14
14
20. Which would be the sim plest formula o f com ­
A) 12 41) 24 C) 32 D) 40 E) 65
pound that analyzes to 75 % by mass o f carbon and
25 % of hydrogen ? C:12, H:1
12. 100 g o f CaX2 contain 20 g Ca. W hat clement
A) CH B )C H 2 C )C H 3 D )C H 4 E ) C 2H 5
does X stand for ? 0 :1 6 , Ca:40, F:19, Cl:35.5, Br:80,
 CHAPTER

The Gaseous State of Matter

(Kinetic Theory)

The objectives of this chapter are to enable the student

to :
1.Describe the general characteristics of gases.
2.Define pressure and describe how it is measured and
e x p re s s e d .
3 .Explain Avogadro's Hypothesis and the molar vol­
umes of gases.
4.Use the kinetic molecular theory to explain the be­
havior of real gases.
5.Calculate the effect of changes in pressure, volume
and temperature on a gas sample.
6 .Explain the origin of the universal gas constant R.
7 .Find the number of moles of gas in a sample when its
volume, pressure, and temperature are given.
8 .Find the molecular weight of a gas given its density
at a given pressure, and temperature.
9 .Find the molecular weight of a gas when its rate of
effusion relative to a known gas.
lO.Explain partial pressure of a gas in a gas mixture.
 The Gaseous State o f M atter (Kinetic Theory) 07

G ases are the sim p lest form o f m atte r in m an y w ays, and th e ir p h y sical
p ro p erties are easy to understand. T he m o lecules o f a gas are relatively apart,
an d th ey are in a to ta lly random m o tio n . T h e fo rce s o f a ttra c tio n b e tw e e n
m olecules are so sm all that each m olecule m oves freely and behaves as though
the o th e r m olecules w ere n o t present. T h erefo re the in v estig atio n o f the p ro p ­
erties o f gases is m u ch easier than th o se o f liq u id s and solids. T h e law s that
go v ern th e b e h av io u r o f gases h av e p la y ed an im p o rtan t role in the d ev elo p ­
m en t o f th e atom ic theory o f m atter. In this ch ap ter w e w ill lo o k at the b e h a v i­
o u r o f gases to understand the structure o f m atter.

3.1 GENERAL PROPERTIES OF GASES

3.1.1 PRESSURE
A gas expands to fill any container because gas m olecules are in constant
m o tio n . F u rth erm o re, in the co u rse o f th eir random m o tio n , gas m o lecu les
strike th e w alls o f th e ir container. B ecause o f these collisions gases ex ert p re s­
sure. S ee F ig u re 3.1.
P ressu re is defined as force p e r u n it area.

P ressu re - F orce
Area A
FIGURE 3.1 д gas con­
sists of billions of billions T h e p ressu re o f a gas is d irectly p ro p o rtio n al to the n u m b e r o f collisions
molecules in random mo­ on a u n it area, the ad dition o f som e m o re gas to th e co n tain er, o r d ecreasin g
tion. Because of the colli­ volum e o f the container, o r increasing tem perature o f the gas increase the p res­
sions of gas molecules
sure o f a gas.
with the wall of the balloon,
a pressure is exerted, and 3 .1.1.1 U N IT S O F P R E S S U R E
the elastic wall of the bal­ (1) P ascal : T h e SI u n it o f p re ssu re is th e p a sc a l (a b b re v ia te d Pa)
loon expands.
w h ich is d efin ed as the pressu re eq u iv alen t to a fo rce o f 1 n ew to n
(1 N = 1 kg jm /s2) acting on one square m eter.

l P a = iN i k g m / s _2 = lk g /m s 2
Gas pressures are 1m 1m
most commonly ex­
pressed by chemists (2) A tm o sp h ere : O ne stan d ard atm o sp h ere ( ab b rev iated 1 atm ) is
in units of atm or
th e p ressu re exerted by a co lu m n o f m ercu ry th a t is 760 m m high at a te m ­
rrtmHg ,
perature o f CFG
(3) M illim eter o f m ercu ry : O ne m illim e te r o f m e rc u ry ( a b b re v i­
ated- m m H g) is the pressure exerted by a colum n o f m ercury 1 m m in height.
1 atm = 760 m m H g (0°C)

(4) T orr : T h e torr is 1/760 o f a stan d a rd a tm o sp h e re. T h e to rr,

and m m H g are the sam e. T h e atm o sp h ere, and m m H g are the u n its w h ich
w e use th ro u g h o u t this book.
1 a tm = 76 c m llg = 760 m m H g = 760 to rr
08 Chapter 3

E X A M P L E 3.1 I n t e r c o n v e r tin g U n its o f P r e ssu r e

Problem .'C onvert
a) 684 mmHg to atm b) 0.75 atm to cmHg c) 1.25 atm to torr
Solution :
a) 684 mmHg x - 1 alm— = 0.9 atm b) 0.75 atm x 76 cmHg = 57 cmHg с) 1.25 atm x 760 1017 = 950 ton-
760 mmHg 1 atm b 1 atm

EXERCISE 3. 1 Perform the following unit conversions

a) 1330 torr = ? atm b) 2 atm = ? mmHg c) 190 cmHg = ’ aim

3 .1 .1 .2 M E A S U R IN G PRESSURE
a) A tm o sp h e r ic P r e ssu r e
W e live at the bottom o f a gas m ixture, atm osphere. T he m olecules o f air
ex e rt a p re ssu re o n us. T h is is called the o p e n a ir p re ssu re o r atm o sp h eric
p ressu re. A b a r o m e te r is used to m easu re th e p re ssu re th at the atm osphere
exerts o n th e surface o f the earth. A s sh o w n in F igure 3.2, a tube is filled w ith
m ercu ry and inverted in an op en c o n ta in er o f m ercu ry .S o m e o f the m ercu rey
flow s out o f the tube until the pressu re exerted by the atm osphere on the m er­
cury in th e dish is exactly balanced by the pressure o f the m ercury in the tube.
O r the w eig h t o f the m ercury co lu m n rem aining in the tube is supported b y a t­
m osp h eric p ressure acting on the surface o f the m ercury.
Patm = h (the len g th o f m ercu ry colum n)
Han barometer. When a
mecury filled tube is in­
T h e m agnitude o f the standard atm ospheric pressure is equal to the p re s­
verted in a dish of mercu­ sure w h ich supports a colum n o f m ercury exactly 76 cm high at sea level. B ut
ry, the level of the mercu­ the a ctu al atm o sp h e ric p re ssu re d ep en d s on b o th lo c a tio n and o n w h e ath er
ry in the tube falls, thus conditions.
leaving a vacuum at the
top of the tube. The
M eteo ro lo g ists use the chan g es in p re ssu re to fo re cast w heather. S ince
height of the mercury col­ w ater v ap o r (M W = 18 g/m ol) has a lo w e r d en sity th an the air, (average M W
umn is determined by the = 29 g /m ol) "w et air" exerts a lo w er p ressu re th an dry air. T h erefo re, an a p ­
pressure of the atmosh- p ro ach in g fro n t o f low p ressu re m ean s the approach o f m oistu re - lad en air,
pere. o r a probable precipitate.
E X A M P LE 3.2 C a lc u la tin g P r e s s u r e
Problem : Calculate the height of the water column in a barometer for 1 atm pressure if water is used instead
of mercury. d n g = 13.6 g/mL.
Solution .The difference in heights arises from the differences in the densities of water and mercury. The pres­
sure exerted by 1 cm mercury column can be established by 13.6 cm of H2O column because dng = 13.6 x dn2o
1 atm pressure or 76 cmHg pressure will be exerted by:

76 cmHg x 13,6 cmH.2.Q = 1033.6 cm H20 = 10.3 m H 20

1 cmHg

EXERCISE 3.2 A barometer reading is 76 cmHg at sea level at 5°C. If this barometer is taken 136 cm
below the sea level at 5°C, what will be its reading ? d n 2o = 1 g/mL dug = 13.6 g/mL 86 cmHg
 The Gaseous State o f M atter (Kinetic Theory) 09

b) G a s P r e ssu r e
A m a n o m e te r is used to m easu re the p re ssu re o f a gas in a clo sed c o n ­
tain er. T h e re are tw o ty p es o f m a n o m e te r : O p e n -e n d m a n o m e te r a n d ...
c lo s e d - e n d m a n o m e te r .
1. In a clo sed end m a n o m e ter, as sh o w n in F ig u re 3.3 th e d o w n w ard
p ressure ex erted by the co lu m n o f m ercu ry is balan ced by th e p ressu re o f the
gas in the flask. H en ce the h eig h t o f the m ercu ry co lu m n show s d irec tly the
pressure o f the gas.
* gas = h
2. In an op en end m an o m eter w e should lake the op en a ir pressure into
c o n sid e ra tio n . I f the le v e ls o f m ercu ry arc th e sam e in b o th arm s o f the U
tube, the p ressures on both sides arc equal. (Sec F ig ure 3.4)
| P gas(in the flask ) = P aa tm
FIGURE 3.3 /\ closed- If the level o f m ercury in the left colum n is higher, then Palm>P,gas
end manometer. The
pressure of the gas is atm
determined by measur­ I f the level o f m ercury in the righF hand colum n is h ig h er than in the left-
ing the differences in
hand colum n, then Pgas>Paim
heights of the two mer­
cury columns in the arms I i!.f> ' P.lllll
of the U tube. Pgas=h

mercury

\ FIGURE 3.4 Open-end manomete}

E X A M P L E 3.3 R e a d in g M a n o m e te r s
Problem : List the pressures of the following gases in increasing order. (PaIm = 76 cmHg)

Solution : In a closed end manometer Pgas = h, therefore Р д = 76 cmHg. In an open-end manometer, the pres­
sure in the arm of the U tube (in which the level o f mercury is lower) is greater. For the gas B, the levels of mer­
cury b n both arms are equal therefore Pg = Palm. For the gas C, Patm> P c and P c = Paim - h = 76 - 76 = 0 or we
70 Chapter 3

may deduce that there is no gas in the bulb С (vacuum). For the gas D, Pq ^ Patm and
Pd = Patm + h = 76 + 50 = 126 cmHg. So the order o f pressure of gases are :
Pc = 0<Рд = P b = 76 cmHg<PD = 126 cmHg

E X A M P L E 3.4 Measuring the Pressure of a Gas

Problem : The pressure of gas A is measured with a manometer, and then the open - end of the manometer
is connected to the gas B, and the levels o f mercury columns change as shown in Figure II. W hat is the pressure
o f the gas В ? Patm=76 cmHg
A

у
h=20 cm H g h=20 cm H g

Solution : First manometer is open - end manometer and the pressure of the gas A is greater than Patm.
PA = Patm + h => PA = 76 + 20 = 96 cmHg
In the second one: PB > PA , PB = PA + h => PB = 96 +20 = 116 cmHg

EXERCISE 3.3 Find the increasing order among the pressures

j p 0 Pq, P], ?2 >n Figure 3.6

mercury
I P l > P 2 >Po

EXERCISE 3.4 The pressure oi the gas С is 70 erriHg. Determine PA, PB and Patm.
Patm

" i- U
hj= 20 cmH g.
'J
h2= 30 cmb g.
-h
Ьз= 68 cmH20

( !>A = 9 5 c m H g , Pff=65cmHg, Patm= 7 5 c m H g )

 The Gaseous State o f M atter (Kinetic Theory) 71

3 .1 .2 K IN ETIC TH EO RY O F G A S E S
G ases h av e no fixed shape o r volum e. T h e volum e o f a gas is alw ays the
sam e as th e volum e o f its container. B ecause gases consist o f w id ely separated
m olecu les in rapid m otion. T h e y alw ays spread out to fill w h atev er space they
h av e available. T h e continuous m otion o f a gas show s th at gas m olecules have
a great deal o f energy.
T h e energ y o f m otion is called the kinetic energy and form ulated as
1 2
KE = - mu w here, m = m ass and v = v elo city
2

T h e e n e rg y o f m o le c u le s c a n b e ch a n g e d in c o llisio n s.
T herefore the speed as w ell as the d irectio n o f a m o lecu le change
continually. W e m ay sp eak o f an average speed. S ince the m o le ­
cu les h av e an average speed th ey m u st h av e an av erag e k inetic
en ergy.
W h en the te m p eratu re o f a gas is in creased , the n u m b e r o f
gas m olecules th at m ove at the h ig h er speeds increases. B ecause
f ? \ Т ^her increasing the tem perature o f the gas increases the average kinetic
\ \te m p e ra tu re
I e n erg y o f the gas. D istrib u tio n s o f the m o le cu lar speeds o f a gas
J \
-L o w er 4 4 at tw o tem peratures are show n in F igure 3.5.
te m p e ra tu re ж
1L T he regularities in the behavior o f all gases have led to a the­
M olecular speed, n o ry . T h is th e o ry , c a lle d th e k in e tic m o le c u la r t h e o r y , is
FIGURE 3.5 Distribution of molecu­ b ased on som e fundam ental assum ptions w h ich serve as a m odel
lar speeds at two different tempera- fo r explaining the properties o f gases.
T h e k i n e t i c th e o r y o f g a s e s h a s th e fo llo w in g a s s u m p tio n s .
1. G a se s a re c o m p o se d o f m o le c u le s o r a to m s w h ic h h a v e n e g lig ib le
vo lu m e in co m p a risio n to the to ta l vo lu m e o f the gas. In o th e r w o rd s the gas
m o le c u le s can be co n sid e re d to be p o in ts w ith m a ss b u t w ith n eg lig ib le v o l­
um e.
2. G as m olecules are in constant, rapid, straightline m otion.
3. M o lecu les collide w ith each o th er a n d w ith the container w a lls b u t the
collisions are totaly elastic so that no kinetic energy is lost.
4. T he a verage kinetic energy o f the m olecules o f a ll gases is the sam e a t
a g iven tem perature, an d is directly p ro p o rtio n a l to the absolute (K elvin) tem ­
p erature. K E a T
5. The attractive or repulsive fo r c e s betw een m olecules are negligible.

3.1 .3 . G R A H A M 'S LA W OF D IFFU SIO N

The sp re a d o f a gas m o lecu les th ro u g h o u t a space, o r th ro u g h o u t a se c­
o n d gas by virtue o f their kin etic energies is ca lle d the d iffu sio n o f the gas.
S u p p o se th at the g ases A and В are in tro d u ce d se p a rate ly in id en tica l
c o n ta in e rs at th e sam e tem p eratu re and p ressu re. A cco rd in g to th e k in etic
72 Chapter 3

theory gases at the sam e tem perature have the sam e average kinetic energies.
К Е д is the average kinetic energy o f the m olecules o f A
K E b is the average kinetic energy o f the m olecules o f В
K Ea = KEB
I f m A, m g, d a and \>в represent the m asses and velocities o f A and В gas
m olecules, w e m ay w rite
2
2 2 mB
1 1 1 z «А . W \.
— m Au A- —m B\) B or m Au A = m gUB-
2 mA V mA

T h e ratio o f the m o lecu lar m asses, т в / т А, is the sam e as the ratio o f the
m olecular w eights, M W B/M W A,and then,
MWt
^ л Г ^ - J
Stopcock closed
Vi rnA
n iA vi MWA v.

N o w su p p ose th at each con tain er has id en tical v ery sm all o p e n in g in it.

G as m o le c u le s w ill esc a p e th ro u g h th ese o p en in g s. The m ovem ent o f gas
molecules through an extremely small opening into a region o f lower pressure
is c a lle d the e ffu s io n .
The rates o f diffusion (or effusion) o f two different gases are inversely
proportional to the square roots o f their m olecular weights. This is k n o w n as
Stopcock open G r a h a m 's L a w o f diffu sio n .
T he tim e interval in w hich a gas effuses through a sm all hole is inversely
p roportional to the rate o f effusion o f the gas. T herefore for gases A and B.
Va _ tB

и в 1a
o r in a com pact form w e m ay w rite
:_ t g . / M W T .
DB ta
lA V
» iviW
M vv A V dA
T he densities o f gases u n der the sam e conditions are directly proportional
to th eir m o lecu lar w eights.

E X A M P LE 3.5 Using the Law of Effusion

Problem : W hat is the ratio o f molecular weights of gases X and Y if X molecules show an average veloci­
ty of 6 x l0 4 em/s at 300°C and Y molecules show an average velocity o f 4 x l0 4 cm/s ?
Solution ;
=» N TV V x _ ( 4 \ l o V _ 16 _ 4

MWV 2 \ |W MWV , 42 36 9
t)x y } (6x10)

EXERCISE 3.5 If the average velocity of an oxygen molecule, O 2, is 4.2 5 x l0 4 cm/s at ()°C, what is the
average velocity o f a CO 2 molecule at the same temperature ? 3 . 6 2 x l 0 4 cm/ s
 The Gaseous State o f M atter (Kinetic Theory) 73

E X A M P L E 3.6 Comparing Diffusion of Gases

Problem : nh3 hci

b " 6
Two pieces o f cotton, one soaked with NH 3 solution and the other with HCI solution, are inserted into the open­
ings of a glass tube of 1 m length simultaneously. W here the vapors o f NH 3 and HCI meet a white cloud of
N H 4CI (s) forms. W here will the white cloud be formed in the tube ? NH3:17, HC1:36.5
Solution : Since MW of N H 3 is smaller than MW o f HCI, then NH 3 molecules will move faster than HCI
molecules. But how much faster ?
t>NH,
V>H
О н f'i
а V MWmi
» M W M , 3 Dun
X ) HC1 V 17
or dnh 3 = 1.47 x uhci
in a unit time if HCI takes one unit of distance, NH 3 will take 1.47 unit of distance.

100 cm x L47 cm/s = 59.5 cm

2.47 cm/s
So the white cloud will be formed 59.5 cm from the end of NH3.

E X E R C IS E 3.6

H c - f r ) ) ) ) 4 ) f 5 0 2

I II III i>
W here will these gases meet in the tube ? Hc:4, S 0 3:64 IV

3.2 GAS LAWS

3.2.1 A V O G A D R O 'S LAW (M o le -V o lu m e R e l a t i o n s h i p )
S o lid s and liq u id s h av e d e fin ite v o lu m e s and th e ir v o lu m e s do n o t
c h an g e c o n sid erab ly w ith th e tem p eratu re and p re ssu re change. B u t the v o l­
u m es o f gases vary w ith tem perature and pressure. A s stated b y A m adeo A vo-
gadro, an Italian scien tist (1776-1856), th e v o lu m e o f a gas is p ro p o rtio n a l to
th e n u m b ers o f gas m o lecu les, o r m oles n o t to the m asses o f the m o lecu les at
c o n stan t tem p eratu re and pressure. T h e m o d e m form o f this fact is k n o w n as
A v o g a d r o 's L a w . S ee F igure 3.6. The volum e o f a g a s u n d e r c o n sta n t te m ­
p e ra tu re a n d p re ssu re is directly p ro p o rtio n a l to the n u m b er o f m o les o f gas,
th a t is,
V, n,
V a n => — = — (P a n d T constant)
n2

I f th e v o lu m e s o f tw o gases u n d e r the sam e c o n d itio n s o f tem p e ra tu re

fa w URE 3 -6>4vogadro s ^ pressure are the sam e, (V 1 = У г ). then w e m ay deduce th at the m ole n u m ­
b ers o f th e se tw o g ases are the sam e (n i = П2). T h e re fo re A v o g a d ro 's L a w
74 Chapter 3

m ay b e exp ressed as follow s.

Equal volumes o f gases contain equal numbers o f moles at the sam e tem­
perature and pressure.
R e m e m b e r that the v o lu m e occupied by one m o le o f any gas u n d e r th e
stan d ard c o n d itio n s o f te m p eratu re and p ressu re o r S T P is 2 2.4 liters. T h is
volum e is called the standard m olar volum e .
M o la r V o lu m e = 2 2 .4 L /m o l at S T P .

E X A M P L E 3 .7 ^ C a lcu la tin g M o le c u la r W e ig h t, U sin g A v o g a d r o ’s H y p o th e s is

Problem : 16 g o f S 0 2 occupy 20 liters. A t the sam e pressure and tem perature 60 gram s o f an unknow n gas
occupy 60 liters. W hat is the m olecular w eight o f the unknow n gas?
Solution : W e w ill solve this problem by using A vogadro’s H ypothesis. F irst w e will find the m o le num ber
0 fS ° 2 пю =— = _ > 6 j L _ = o.25 mol
2 MW 64 g/m ol

At the sam e conditions V a n

If 20 liters o f S 0 2 (any gas) contain 0.25 mol 1 T _ 60 L x 0.25 m o l _ () 7 5 mQj
60 liters x J 20 L

0.75 is also the m ole num ber o f the unknow n gas. T he w eig h t o f the unknow n gas is given. Then w c can calcu­
late its M W fi()
n=_ _ => MW = — = — s— = 80 g/m ol = M W of the unknow n gas
MW n 0.75 mol
л --------------------------------------------------------------------------------------------------------------
EXER C ISE V3..7 114 gram s o f hydrogen gas occupy 20 liters, w hat will be the volum e o f 33 gram s of
C 0 2 gas a t the sam e conditions ? 7.5 /,

r r
\
EXERCISE $.8 The f igure given aside show s a graduated cylinder with a freely m ovable piston. The cy l­
inder contains 2 g o f fly at the m om ent. Find the volum e o f the gas in the cylhfder
2^ after each of the follow ing changes has been m ade at constant tem perature.

Jd
^ a) addition of 2 g of fly to the cylinder
rL b) rem oval of I g of fly from the cylinder
2L
2gH2 1L c) addition o f 16 g o f Oy to the cylinder
/ " _______________________ __________________________________________ a)4l. h) l l . tl.t/.
EXAMPLE 3 .8 C a l c u la t i o n o f M o le c u la r W e ig h t, U sin g A v o g a d r o 's H y p o th e s is
Problem : A vessel that can hold 8 grains o f oxygen, can hold how m any gram s o f X at the sam e conditions
o f tem perature and pressure? The m olecular w eights o f oxygen and X are 32 g/m ol and 48 g/m ol respectively.
Solution : A vogadro’s H ypothesis w ill be used for the solution o f this problem . At the sam e conditions,
equal volum es o f gases contain equal num bers o f m oles.
m o, mx g it m*
nо = nx 2- = ------- = > s — = ------- — ~ ?=> m , = 12 g
MWo MW, 32 sr/mol 48 ц/m ol
j -----------------------------------------------------------------------------
EXERCISE 3.9 Equal volum es of O 2 and G gases w eigh 0.8 g and 3.65 g respectively. C om pute the m o ­
lecular w eight o f the gas G. 0 :1 6 146 g/mol
 The Gaseous State o f M atter (Kinetic Theory) 75

EXERCISE 3.10 a container which has an airtight and movable piston contains 3 g of H 2 (g). If 42 g of
the gas X 2 is added to the same container at the same temperature the volume of the gas doubles. What is the
atomic weight of X ? H:1 ^ 14 g/mol

3.2.2 B O YLE'S LAW (Pressure • Volume relationship)

T h e re la tio n sh ip b etw e en p re ssu re and v o lu m e at c o n sta n t te m p eratu re
w as first in v estig ated by R o b ert B o y le in 1662. B o y le sta te d th a t a t co n sta n t
tem perature the volum e o f a given m a ss o f gas is inversly p ro p o rtio n a l to p r e s ­
sure, u n d er w hich it is m easured. See F ig u re 3.7. O r,
V a — or P x V = c o n s t a n t
P
In o th e r w ords fo r d ifferen t co n d itio n s o f a fixed am o u n t o f gas th e P x V
p ro d u ct is constant.
P ,V i = P2 V 2 = P3 V 3 = PnV„ = constant

Pi = 1 atm P2 = 1.5 atm P 3 = 2 atm P4 = 6 atm

x Vj = 6 L V2 = 4 L V3 = 3 L V4 = 1 Lt
Pj V j = 6 P2V 2 = 6 P3V 3 = 6 P4V 4 = 6

FIGURE 3.7 A graphical illustration of Boyle's Law. Note how the volume decreases as the
pressure increases, but P V product always remains constant.
i

E X A M P L E 3.9 Understanding Behaviour of a Gas and Boyle's Law

Problem : A cylinder with a rpovablc piston contains V liters of gas at a certain temperature and pressure. If
the piston is pushed down until the volume of the gas is 0.5 V liter, compare the following
properties ol' the gas for the initial and final situations. (Assume the constant temperature)
a) the number molecules b) density c) the average kinetic energies of the molecules
d) the frequency of collisions between molecules e) pressure
Solution : a) The number of molecules of the gas does not change. Because there is no
gas entrance to or exit from the cylinder.
b) d = — Since the mass of die gas remains constant, and the volume decreases by one half, then the density
of the gas doubles.
c) KE a T. The temperature is the same for both situations. Hence theaverage kinetic energies o f the molecules
is the same for both situations.
d) In the final situation the same number of molecules arc compressed to a smaller volume. This increases the
probability of the confrontation o f molecules. Thus the frequency o f collisions increases.
e) In the final stuation the number of collisions between molecules and the walls o f the container doubles. As a
result the pressure doubles. You may reach the same result by using the formula P| V j = P 2V2.
76 Chapter 3

E X A M P L E 3 .1 0 C a lc u la tin g w ith th e B o y le 's L aw

Problem : The volume of a gas is Found to be 200 mL under a pressure of 750 mmHg. If the pressure were
changed to 500 mmHg, what would be the new volume ? (Assume constant temperature)
Solution : First, we should tabulate what is given and what is required ?
final conditions Since the temperature and the mass of the gas are constant, then
Original conditions
P 2 = 500 mmHg we shall use Boyle’s Law to solve the problem. As the pressure
Pi = 750 mmHg
V2 = ? 1 of a gas decreases the volume of the gas increases. By reasoning
V j = 200 mL
we see that the pressure is decreased by a factor o f 500/750.
Hence the volume of the gas must be increased by the reverse
of this factor, 750/500. Thus we may obtain the final volume by multiplying the original volume by 750/500.
That is
V 2= V , x 750/500 => V 2= 200 mL x 750 nlmHg = 300 mL
2 1 500 mmHg

Or we use the equation PjV 1 = P 2V 2 to obtain the new volume,

750 mmHg x 200 mL = 500 mmHg x V 2 => V 2 = 300 mL

EXERCISE 3.11 A gas has a volume o f'300 mL under a pressure of 720 mm of mercury. II the tempera­
ture remains constant, calculate its volume under a pressure of 540 mmHg. 400 mL

EXER C ISE 3.12 A column of air 7 cm in length is trapped in a tube

} i by placing a plug of mercury column of 5 cm length (sec Figure I). When tlie

К
5 cm
tube and its contents arc inverted figure 11 is obtained. Calculate the height of
^ cm the air column in figure II. Assume the atmospheric pressure is 75 cmHg.
Ji cm

3.2.3 C H A R L E ’S LAW
(The Tem perature-Volum e Relationship)
V (L)
It h as b een know n that a decrease in the tem p eratu re o f a substance ca u s­
es th e m olecu les o f the substance to m ove m ore slow ly o r vice versa. T em p er­
atu re, then, is a m easu re o f the averag e k in etic en erg y o f the m o le cu le s o f a
sub stan ce. It should in theory be p o ssib le to lo w e r the tem p eratu re to a p o in t
w h ere all the m o tio n o f m o lecu les stops. T h is te m p e ratu re is called absolute
zero, -273. 15°C (usually rounded to -273°C )

FIGURE 3.8 j h e rela­ T he v o lu m e o f the gas increases 1/273 o f its v alu e at 0° fo r ea ch C elsius
tionship between tem­ d eg ree rise in tem p eratu re at co n stan t pressure. A lth o u g h the v o lu m e o f a gas
perature and gas vol­ in creases in reg u lar m an n er w ith increasing tem perature, the vo lu m e is n o t d i­
ume. As the temperature re c tly p ro p o rtio n a l to the C elsiu s te m p eratu re. F o r ex a m p le, in c re a sin g the
increases by 1°C, the tem p eratu re form 0°C to 10°C increases th e v o lu m e from 274 m L to 283 m L
volume of the gas in­ n o t to 284 m L . B ut the volum e o f any sam ple o f gas is directly p roportional to
creases by 1/273 of its
th e K elv in (ab solute) tem p eratu re at co n stan t p ressure. T his fact is k n o w n as
volume at 0°C
C h a rles' L a w . See F ig u re 3.8.
AV = V „ x — x At
273
 The Gaseous State o f M atter (Kinetic Theory) 77
V (L)
(n, P co n stan t) V i= Ti
V i= V 2
V a T or
Ti T 2 V2 T2

R ecall that К = °C + 273

F ig u re 3.9 sh o w s th a t the vo lu m e o f a g iven q u a n tity o f ga s is directly
Ti т 2 т (K) pro p o rtio n a l to the absolute tem perature. Since volum e is directly proportional
FIGURE 3.9 A graphical to absolute tem p erature, theoretically it should b e zero at absolute zero. Practi-
representation of Charle's cally this can n ev er be achieved, because gases becom e liquefied before they
Law. Theoretically gas vol- reach a tem p erature o f -273.15°C .
ume should be zero at О К . .

E X A M P L E 3.11 C a lc u la tin g w ith th e T e m p e r a tu r e - V o lu m e L aw

Problem : A gas has a volume of 75 mL when measured at 27°C. If the temperature were changed to 127°C,
what would be the new volume ?
Solution : We will tabulate what is given and what is required. We then change the centigrade temperature to
Kelvin temperature. V olum e Tem perature
Initial conditions : V \ - 1 5 mL Tj = 27°C = 300 К
Final conditions : V2 = ? T 2 = 127°C = 400 К
By reasoning we see that the temperature is increased by a factor o f 400/300 since the volume o f a gas changes
directly with absolute temperature the volume, then, must increase by the same factor, 400/300. Or

V 2= V ; X ^ ^ V 2= 7 5 r a L x ^ r 100 mL
300 300

The problem may be solved by using the formula

v i T2 „ T2 400 К .
— = — =s> V 2= V i x — => V 2= 75 mL x = 100 mL
V 2 T, T, 300 К

EXER C ISE 3.13 A sample of C 0 2 has a volume of 120 mL at 273°C, what would be its volume at
standard temperature ? Assume constant pressure. 60 mL

E X A M P L E 3 .12 U n d e r s ta n d in g C h a r le 's L aw .
Problem : The volume - temperature change of a certain am ount o f gas at
constant pressure is shown graphically in figure given aside. W hat volume will
the gas occupy at -73°C and at the same pressure ?
Solution : From the graph, we may see that the volume of the gas is 12.3 L
at 27°C.

V olum e T e m p e r a tu r e

Initial conditions :V 1 = 12.3 L Tj = 27°C = 300 К j

V J i. V 2= V ,x — =» V 2= 12.3 L x = 8.2 L
Final conditions :V 2 = ? T 2 = -73°C = 200 К -» v 2'V T, 300

EXER C ISE 3.14 A sample of He occupies 5 L at 127°C. Calculate the temperature in °C at which the
gas will occupy 0.5 L at constant pressure. -233°C
78 Chapter 3

3 .2 .4 G A Y -L U S S A C 'S LAW
T he volum e o f gas placed in a container increases w hen a gas is heated.
The p re ssu re o f a g iven sa m p le o f a gas varies d irectly w ith k elvin tem ­
p e ra tu re i f th e volum e is kep t constant. See F igure 3.10.

Pi Pi : Ti
p—2 o r ----
FIGURE 3.10 A gra­ Ti T2 P2 T 2
phical representation of
Gay Lussac's law.

E X A M P L E 3.13 C a lc u la tin g W ith the T e m p e r a tu r e - P r e ssu r e L a w

Problem : In a closed container there are 4 grams of 0 2 gas under 1 atm pressure. If the temperature of the
gas is increased from 0°C to 273°C, what will be its pressure ?
Solution : W e will tabulate what is given and what is required
P, = 1 atm T | = 0°C = 273 К 1 Pi _ T , p __p v T2 546 К
} _ i = — => p 2 = P j x — => P 2= 1 atm x — —— = > P 2= 2 a tm
P2 = ? T 2 = 273°C = 546 К JJ P 2 T‘ 22 T*1, 273°C

EXERC1SE(3.15 In a 20 L. container there is a sample of a gas at 27°C and 4 atm pressure. To decrease
its pressure to 2 atm, the temperature must be reduced to what centigrade degree ? -I23°C

3.2.5 ID E A L G A S LAW
So fa r w e have d iscu ssed the re la tio n sh ip s b e tw ee n the v o lu m e , m ole
n um ber, pressure, and tem perature fo r specific conditions. A general equation
m ay be d eriv ed that relates the vo lu m e, m ole num ber, p ressu re, and tem p era­
ture. L et us see how to derive this equation
V (X П (Avogadro' s Law)

V a (Boy l e ' s Law)

V a T (CharlesLaw) co m bining th e se law s w e o b tain

V a n x —x T
P
T o c h an g e this p ro p o rtio n ality into an eq u ality , w e should in se rt a p ro ­
portionality constant (R ) into the proportionality. T h a t is

v =R X 3 -lZ => P V = n R T
P
T h e eq u atio n , P V = n R T , is k n o w n as the equation state of gases o r
the ideal gas equation. In this eq u atipn.
------------------> P ressure (P)
> m ole num ber
I » T em perature (K)
3V = nR T
^------- > Ideal gas constant
7 > V olum e (L)
 The Gaseous State o f M atter (Kinetic Theory) 79

T h e v alue o f the ideal gas co n stan t m ay be found by th e fac t that 1 m ole

22.4 L atm
R = o f any gas occupies a volum e o f 22.4 L at ST P, 0°C and 1 atm.
273 mol К
At S T P
R : 0.82 L atm mol К
n = 1 m ol
P = 1 atm , PV 1 atm x 22.4 L 22.4 L atm L atm
R = 0.082
V = 22.4 L
T = 273 К } ’ nT 1 mol x 273 К 273 mol К mol К

EXERCISE 3.1 6 Prove that the" value of R to be 62.3 mmHg L/mol К (0 °C = 273.15 K)
T h e ideal gas equation unites the gas law s o iA v o g a d ro , H oyle. C harles
and G ay L u ssac in one equation. T h erefo re it is a co m p lete d e scrip tio n o f an
ideal gas, and is then one o f the m o st useful eq u atio n s in ch em istry . A very
larg e n u m b er o f p ro b lem s can be solved by u sin g the id eal gas eq u atio n . If
three o f the four unknow ns are specified the value o f the fourth can be found.
O n th e o th e r han d w e can o b tain new rela tio n sh ip s by co m b in in g the
ideal gas eq u atio n w ith the ex p ressio n s th at defines the m ole n u m b er, n. R e ­
call that n = m /M W . By substituting this expression for n in PV = nR T
we g e t:
PV RT
MW
T his equation is im portant especially in determ ining the m olecular w eight
o f a gas.
Som e o f the calculations about ideal gases involve the calcu latio n o f the
gas density. W e can arrange the equation in a form that covers the gas density
d = m /V o r m = d x V fo r gases : m —> the m ass o f the gas in gram s,
V —> the volum e o f the gas in liters
By su bstituting dxV for m in the equation , PV = - L_ r t ,gives
3 MW
dV
PV =- RT
MW
C ancelling the V 's o n both sides o f the equation w e g e t :

p _dК T l « * W /
or PM W = d R T
MW

and tem p erature o f a given am ount o f gas. In such problem s w e w rite the ideal
gas equation for tw o conditions
fo r first co nditions :P XVi = nR T , , and for second conditions : P 2V 2 = nR T 2
Since the am ount
P jV i nRT o f gas is constant
approportionating them tcn u by term gives its m o le n u m b e r
P 2V 2 nRT 2

Sim plifying the equation gives P tV t T, P ,V , _ P 2V 2 I

or
P 2V 2 T2 T, T2
T h is e q u a tio n is k n o w n as c o m b in e d g a s e q u a tio n .
 80 Chapter 3

Ideal G ases, Real Gases.

W c h av e assum ed that m o lecules o f a gas do n o t ex ert any force, either
attractiv e o r rep u lsiv e, on one another, and they are "p o in ts” w ith m ass b u t
w ith o u t v o lu m e. A gas th a t satisfies th ese co n d itio n s is said to b e an id ea l
gas. A n ideal gas obeys the law s m entioned so far. It is o b vious th at these as­
sum ptions arc quite unsatisfactory. F o r exam ple, w ithout in te rm o le cu la r fo rc ­
es co u ld g ases co n d en se to form liquids ? T h e re fo re alm o st all g ases (real
g a ses) fail to o b ey the id eal gas b e h a v io u r to a g re a te r o r le sse r extent. T he
im portant question is : U nder w hat conditions will gases behave ideally. Since
th e forces b etw een m olecules and the volum e o f gas m olecules cause gases to
d ev iate from th e id eal gas b e h av io r, w e sh o u ld lo o k fo r the c o n d itio n s aL
w h ich these forces are negligible. W hen ihe density o f a gas is low th e m o le ­
cules o f the gas are m u ch ap art from one another. T h is m eans a n eg lig ib le
force b etw een m o lecules and n eg lig ib le fractio n o f v o lu m e o f gas m olecu les
w ith respect to the total space available by the gas.T he inspection o f the e q u a­
tion, d = P M W /R T , show s th at gases h a v e lo w d e n sitie s at lo w p ressu res,
and a t high tem peratures. T herefo re, gases b eh av e m o re id eally at lo w p re s­
su r e s and at h ig h tem p er a tu r es (the co n d itio n s w h ic h fav o r a lo w density
o f gas). A w ay to u n derstand w h eth er a gas b eh av es id eally is to lo o k at the
ratio o f P V /R T fo r one m o le o f gas, w hich is ex actly 1. for an ideal gas. See
F igure 3.11.

FIGURE 3.11 Plot of

P V /R T versus P of one
mole of gas at 0°C. The ra­
tio, P V /R T is equal to one
for one mole of ideal gas,
no matter what the pres­
sure is. For real gases, we
observe deviations from
ideality at high pressures.
Note that at low p res­
sures, all gases exhibit al- 0 200 400 600 800 1000 1200 ,

most ideal behavior.

T h e follow ing exam ples illustrate the usage ol the ideal gas equation and
________________ its derivatives in solving pro b lem s._____________________
E X A M P LE 3.14 U sin g the E q u a tio n o f S ta te for an Id eal ( la s
Problem : A sample of a gas exerts 4 atm pressure and its volume is 61.5 liters at 27°C. How many moles
of gas arc there in the sample ?
Solution : Let us tabulate what is given and what is required.
P = 4 atm
V = 61.5 L 4 atm x 61.5 L
PV = nRT => n = — - => n = 10 mol
T = 27°C = 300 К
R = 0.082 L atm/mol К
n=?
} RT
0.082
mol К
x 300 К
 г \ ^
o j y t
(У

The Gaseous State o f M atter (Kinetic Theory) 81

EXAM PLE 3 .15 U sin g Id e a l G a s E q u a tio n

Problem : How many moles gas are there in 547 mL of N 2 at 27°C and 684 mrnHg pressure ?
Solution : Let us tabulate the givens in the problem and do the necessary unit conversions.
P —> atm, V —> L, T—> К
P = 684 111111Hg = 684 mrnHg x — 1 alm— = 0.9 atm
b 760 mrnHg

V = 547 mL - 547 mL x — L t — = 0.547 L

1000 mL
T = 27°C = 27 + 273 = 300 К

PV = nRT => n = ™ = - ° - 9 atm x °-547 L => n = 0.02 mol

RT 0.082 biliH L x 3CK) К
mol К

The problem may be solved by using the value R = 62.3 L mmHg/mol К

In that case the units o f the pressure, volume, and temperature should be mrnHg, L, and K.
n= 684 mmHg x 0 :5 4 7 L = Q ()2 m(j,
62.3 (L.atm/mol К) x 300K

EXER C ISE 3.17 Calculate each o f the following

a) the number of moles of O 2 that has a volume of 4.48 1. at 0 C and 2 atm.
b) the volum e o f 0.25 mol o f SCH at 77°C and 950 torr.
Cj the temperature of 0.2 mol of gas that exerts a pressure of 2280 mmHg in a 4(X)111L closed container,
d) the volume of 0.15 mol of ССЬ at 127%’ and 57 cmHg.
a ) 0 .4,not h)S.74L. c)-2t)0°C d)6.56L

EXAM PLE 3 .16 U sin g the E q u a tio n of S ta te fo r a n Id e a l G a s

Problem : Calculate the pressure exerted by 6,4 g O 2 in a 1 L container at 0°C.
Solution :
P=? First, find the mole number of the gas, and find the pressure by means of the ideal
V =1 L I gas equation.

У n = - I B - ■■ 6 ,4 8 °
T = 0°c
m = 64
}
M W o 2 = 32 g/mol
gJ MW 32 g/m ol

nRT 0 -2 m » l x | f ^ r | il273 K
г = 0 .2 m ol O ,

P —_ _ _ = ------------- .11101 -------- = 4 .4 8 atm

-

V 1L
Note : It is more practical to use 22.4/273 for the value of R when the temperature and volume arc fractions or
multiples of 22.4 or 273. This enables you to do easily the cancellations in calculations.

EXERCISE 3.18 How many grams of gas arc present in each o f the following ? 0 :1 6 , S:32, N:14
a) 300 mL O 2 at 5 atm and 27°C b) 273 L. of NL at 100 torr and ()°C
c) 546 mL of SO 2 al 750 mmHg and 152°C a ) l . 9 S h) 4 4. 9 c ) 0. 9 9

/
82 Chapter 3

E X A M P L E 3 .17 Calculating the M o le c u la r Weight o f a G as

Problem : 6 liters o f a gas measured under a pressure of 740 mmHg and at 22°C weigh 6.72 grams. What is
the molecular weight of the gas ?
Solution :
P = 740 mmHg = 740/760 = 0.97 atm W e may first find the mole number of the gas, then find the
V=6L I molecular weight. We may use the equation

m = 6.72 g I MW = m R T = 6.72 g x 0.082 (L atm/mol K) x 295 К _ 28 ц /то ]

T = 22°C = 273 + 22 = 295 К * PV 0.97 atm x 6 L

EXERCISE 3.19 Find the molecular weight of each o f the following gases
a) A 25 g of a gas occupies a volume of 40 L at 752 mmHg and 59°C.
b) A 104 g of a gas has a volume of 5 L at 3.55 aim and 30°C.
c) A 8 g o f gas has a volume o f 2.45 L. at room conditions (25°C and l atm)
a\l7.2glm ol b)I46glm ol c)S0g/mol

E X A M P L E 3 . 1 8 C alculating the M olecular Weight o f a G as

Problem : 2.7 g of X 2O 5 gas occupy 410 mL volume at 127°C and 2 atm pressure. W hat is the atomic
weight of X ?
Solution : First we will calculate MW of the gas X 2O 5.
V = 410 mL = 0.410 L p v = -H L _ R T
I MW
P = 2 atm I
T = 127°C = 400К > 2.7 g x 0 . 0 8 2 - ^ x 4 0 0 К
I MW = 2 1 * 1 = --------------------2 ^ 1 -------------= 1 0 8 g/mol
m = 2-7 S I PV 2 atm x 0.410 L
MW = ?
X 20 5 = 108 => 2X + 5 x 16 = 108 => X = 14 g/mol

EXERCISE 3 . 2 0 Determine the atomic weight of X in the following compounds.

a) 8 g XH 4 occupy 44.8 L volume at 273°C and 380 mmHg pressure.
b) 1.92 g o f X 3 occupies a volume of 574 mL at 77°C and 2 atm.
c) A 0.326 gram of the gas, C 3X 4 has a volume of 250 mL at 100°C and 76 cmHg.
d) A 3.12 gram o f the gas, HX, occupies a volume o f 500 mL at -23°C and 760 torr.
a)l2ghm>l b)16g/mol c)lg/m ol d)l27glm ol

E X A M P L E 3 .19 C alcu latin g M olecular W eight From Density

Problem : Calculate the molecular weight of a gas which has a density of 1.25 grams per liter at 30°C and
764 mmHg pressure.
Solution :
P = 764 mmHg = (764/760) atm PM W = dRT T otm
, „e „ 1.25 g/L x 0.082 H 2 L x 303 К
d = , '2 5 8 /L E52US_ => MW = 31 g/m ol
T = 30°C = 30 + 273 = 303 К P (764/760) Mm
Note : The density means the mass of 1 L of gas. So you may interpret d as : m = 1.25 g, V= 1L
and use the equation PV = -^L_ x RT to find the result.
MW

\
 The Gaseous State of M atter (Kinetic Theory) 83

E X A M P L E 3.20 C a lc u la tin g D e n sity o f G a s a t N o n sta n d a rd C o n d itio n s

Problem : Calculate the density o f S 0 2 at 37°C and 750 mmHg.
Solution :
D «П U . PMW = dRT or d =
P = 750 mmHg = (750/760) atm rt

T = 37°C = 310 К ,
d= (750/760) atm x 64 g /mo1 _ 2 48 g/L
d=? 0.082 (L atm/mol K )x 310 К
MW = 64 g/mol

EXERCISE 3.21 Calculate the molecular weight of each of the following gases
a) A gas with a density of 1.58 g/L at 380 torr and 0°C.’
b) A gas with a density o f 0.67 g/L at 0.75 atm and 273°C.
c) A gas with a density o f 0.5 g/L at 0.34 atm and -23°C. a)7lg/mol b)40 g/mol c)30g/mol

E X A M P L E ^ I F in d in g M o le c u la r F o r m u la fro m M o le c u la r W e ig h t
Problem : An organic compound has an empirical formula of CH 20 . Its vapor has a density o f 2.68 g/L at
STP. W hat is the molecular formula of this compound ?
Solution : Empirical formula o f the compound is given. To determine the molecular formula we have to
know its molecular weight. Since the gas is at STP there-
Molccular weight can be calculated from density. MW = 22 4 L/mol x d g/L
2 68 g/L x ^ atm x 273 К MW = 22.4 x 2.68 = 60 g/mol
P x MW = dRT=> MW = — = ---------------- 273 mo1 K.------------- => MW = 60 g/mol
P 1 atm
(weight of empirical form u la) x n = weight o f molecular formula
(m of CH 20 ) x n = MW , 30 n = 60 => n =2 Then, (CH 20 ) n = molecular formula (CH 20 )2 = C 2 H 4 0 2

EXERCISE 3.22 Determine the molecular formula of the following :

a) The percent composition by weight of a compound is 38.73 % C, 9.63 % H, and 51.64 % О and the density
of its vapor is 2.77 g/L at STP. Find its molecular formula .
b) 0.3 g of gas having a volume of 300 mL at 0.82 atm and 27°C is 80 % С and 20 % H by mass.
a)C 2H 60 2 b)C2H 6

EXAMPLE 3.22 U s in g th e C o m b in e d G a s L a w
«
Problem : The volume o f a gas is 30 mL under a pressure of 700 mmHg at a temperature of 25°C. W hat
would be the volume if measured under 600 mmHg pressure and at 323°C ?
Solution : This problem is about the comparison of the changes in pressure, volume, and temperature o f a
given amount o f gas at two different set of conditions. To simplest way to solve this problem is to apply the
ideal gas equation to both situations separately, and then approportionate them term by term.
84 Chapter 3

Initallv fin ally

lv l _jTjRTi ^ P iV ^ t ,

}
p
Pi = 700 mmHg P 2 = 600 mmHg
P 2V 2 P 2^2 T2
Vj = 30 mL V2 = ?
Tj = 298 К T 2 = 596 К
The equation we have obtained does not include the ideal gas constant, R. Therefore there is no need to change
the units of pressure into atm, and the units of volume into liters. We can use them in any units in the equation
directly provided they are expressed in the same units.
P,v, T, P,V,T2 70 0 интгНс X 30 m l. x 5 9 6 d t -,M ,
= > V >=; • - ----------------5---------- =-------- ------ - = 70 m L
P 2V 2 T2 P 2T , 600 m m flg x 298/K

EXERCISE 3.23 A g as o c c u p ie d 8 7 0 m L u n d e r a p re s su re o f 7 2 0 m m H g a t a te m p e ra tu re o f 17&C . T h e

next day it was measured under a pressure of 750 mmHg at a temperature of 21°C. W hat volume did the gas oc­
cupy under these conditions ? 547 ml.

EXERCISE 3.24 An ideal gas originally at 0.8 atm and 77°C was allowed to expand until its final vol­
ume, pressure and temperature were 600 mL. 0.4 atm and 27°C. What was the initial volume ? .150 ml .

EXAMPLE 3 . 2 3 U s in g th e C o m b in e d G a s L a w
Problem : 4 grams of oxygen gas exert 300 mmHg pressure in a 400 mL container. If 12 grams of oxygen
gas are added into the container and the volume is expanded to 600 mL at the same temperature, what would be
the new pressure ?
Solution : In itially finally
m ] = 4 g 0 2 = 0.125 mol 0 2 m 2 = 4 + 12 = 16 g 0 2 = 0.5 mol 0 2
P i = 300 mmHg P2= ?
V i = 400 mL V 2= 600 mL
Tj=T T2 = T

PiV] n t R T ] Pi V ] n 2 300 mmHg x 400 mL x 0.5 mol r> Qnr. „

= ---------- => P 2= — —= s => P 2= 800 mmHg
P 2V 2 n 2R T 2 V 2n, 600 mL x 0.125 mo!

EXERCISE 3.25 When 3.2 g of oxygen gas is added into a container which already has 1.6 g o f CH 4
gas at 1 atm pressure and 25°C\ the pressure remains die same in the same volume. Find the final temperature.
• __________________________________________________________________________________ - 12 4 " С
EXERCISE 3.26 In a closed container there arc 3 g of H2 gas under 200 mmHg pressure and 2 0 'C. How
many grams o f oxygen gas must be added into this container to increase the pressure to 400 mmHg at 27°C.
_______________________________________________________________________________________________________________4 5 . 7 6 g

EXAMPLE 3 . 2 4 U s in g th e I d e a l G a s l iq u a tio n
Problem ;T o what temperature must a container at 300 К be heated so that 1/3 of the air inside the container
escapes out at constant pressure ?
Solution : In this kind of problems the volume of the container is accepted constant but the am ount of or
the mole number of the gas decreases. If 1/3 o f the air escapes, 2/3 of it remains in the container . And then':
 85

Initally finally
p1=p p2 = P P iV i n i P T ' i . ' F E^-V^h T i n j T*i
I ------ = ------------ => T 2= ----------- -—-f—= -------
V,=V V2 = V I P 2V 2 n 2R T 2 -Р -гУ ,п2Д n2

T m
Ti = 300K
T 9/3
T2 = ? }
j
^
T 2= 3/3 ™ >l x 300 K =» T 2= 450 К
2/3 mol

E X A M P L E 3 .2 5 Comparing Densities at Different Conditions

Problem : The density o f a gas is 1.43 grams per liter at STP. Calculate its density under a pressure of 740
mmHg at 20°C.
Solution :
Initallv finally P 1 x MW ; _ d | x R x T ] _^ • _ P 2X 2* d i x ^ x T]
d i = 1.43 g/L d2 = ? "1I 2XMW
P2 XMW2 d2x R x T 2 ; 2 P ,x ^ ix ilx T 2
P i = 760 mmHg P 2 = 740 mmHg
T , = 273 К T 2 = 293 K JJ d ;=
P|XT2
, 740 mmHg , М 3 g ^ » 273 К д
760 mmHg x 293 К
, , 3„

EXER C ISE 3.27 A gas has a density of 1.25 g/L at 152 cmHg and 273°C. Calculate the density of the
gas at STP. I*2f5 g/L

3.3 GAS MIXTURES AND PARTIAL PRESSURE

In m o st cases w e en counter w ith m ix tu re o f gases rath er th an a single gas
sam ple. W h a t h ap p e n s to th e p ressu re i f tw o o r m o re n o n re a c tin g g ases are
m ixed. See F ig u re 3.12 w hich show s three one-liter bulbs at 25 °C

9 3 mm I 20 г

0 .0 0 5 0 M o le A ir 0 .0 0 1 1 M o le W a te r V apor 0 .0 0 5 0 M o le A ir
in O n e Liter in O n e Liter + 0 .0 0 1 1 M o le W a te r V apor
t = 2 5 °C t = 2 5 °C in O n e Liter
t = 2 5 °C
(a) (b) (c)

FIGURE 3.12 The partial pressures of g a ses

T h e b u lb in F ig u re 3.12 (a) c o n ta in s 0 .0 0 5 0 m o l o f a ir w h ic h ex erts a
p re ssu re o f 93 m raH g . T h e b u lb in F ig u re 3.12 (b) co n ta in s 0.0011 m o l o f
w a te r v ap o r, w h ich e x erts a p re ssu re o f 2 0 m m H g. I f 0 .0 0 5 0 m o l o f a ir and
0.0011 m o l o f w ater v a p o r are in tro d u ce d into th e b u lb w h ic h h a s th e sam e
v o lu m e in F ig u re 3.12 (c) the m an o m e ter reads a p re ssu re o f 113 m m H g . A s
86 Chapter 3

a result, the total pressure exerted by a m ixture o f gases is the sum o f indivi­
dual pressures exerted by each gas alone at the given tem perature. T h is is
k n o w n as th e law o f p a r tia l p r e ssu r e s o r D a lto n 's L a w o f p a rtia l
T h e p a rtia l p re ssu re o f a p ressu res.
gas in a gas m ix tu re is T h e p re ssu re ex erted by ea ch gas in a m ix tu re o f gases is c alled the
the p re s s u re th a t w o u ld
p a rtia l p r e ssu re o f th a t gas.
b e e x e rte d b y the gas if
it w ere alo n e in the c o n ­ S upp o se th at А, В, С ... are th e gases in a m ix tu re
tain e r. A gas alw ay s e x ­
P T = P A + P B + P c + ...
erts the sam e p re ssu re n o
m a tte r it is alo n e o r to ­ W here P t = total pressure, P A, P B, P c are partial pressu res .
g e th e r w ith o th e r g a se s If n A, n B and n c arc the m oles o f gases A, B , and C, the p artial p ressu re
in a c o n ta in er. T h e re fo re
o f each gas can be expressed as
id e a l gas e q u a tio n m ay
b e u se d to c a lc u la te the n AR T njRT nc R T
P A = — ------ , P B= ~ ------- , Pc= ,
p a rtia l p re ssu re s o f g a s ­ A V V V
e s.
(V is the volum e o f the container in w hich the m ixture o f gas is placed.)

n AR T n BR T n cr R T r t
P t = P a + P b+ Pc+ . . . = — + — + (nA+ n B+ n c + . . . )
V V V V
nxR T
where n x = n A+ n B+ n c + ... or P TV = n x R T
V
T h ere is a sim p le re latio n b e tw e e n total p re ssu re and in d iv id u al partial
pressures. T o set up the relationship betw een P A and P x, let us d ivide P A by P x
: P л _ n A RT/V 1 nA
PT n x RT/V nT
T h e ratio o f the n u m b e r o f m oles o f a gas to the total n u m b e r o f m oles
p re se n t in th e m ix tu re is called the m ole fraction (sh o w n by X).
N ow w e can express the partial pressure o f A as

P/
: X Ax P n

S im ilarly P B = X B x P x and P c - X c x P j ... T h e sum o f m o le fra c ­

tions o f gases in a gas m ixture is equal to one. O r_________
X A + Xu + X c + = 1

E X A M P L E 3.26 C a lc u la tin g P a r tia l P r e s s u r e

Problem : A given gas m ixture consists of 0.1 mol of helium , 0.4 mol of neon, and 0.2 mol o f argon. If
the total pressure of the sample is 350 mmHg, what is the pressure exerted by the helium ?
Solution :
Px = 350 mmHg
nx = 0.1 + 0 . 4 + 0.2 = 0.7 mol EilS = => P lle = — x P T= ( U mo1 x 350 mmHg => P „ e = 50 mmHg
Px nx n, 0.7 mol
Pile = ■
nj[e = 0 . 1 mol
 The Gaseous State o f Matter (Kinetic Theory) 87

EXAMPLE 3 .2 7 C a lc u la tin g P a rtia l P re ssu re

Problem : There are 3.5 g of N 2, 0.25 mol of O 2, and 9.03 x 1023 atoms of He gas, at 0°C in a 2.24 liter
container. Calculate the partial pressure of oxygen gas and the total pressure.
Solution : When the temperature and the volume arc given the partial pressure of a gas can be calculated by
using ideal gas equation, because the other gases in the mixture do not affect the pressure of a gas.

d \/ d -г _ d n oJ*T 0.25 m o l x 0.082 (L a t m / m o l K) x 273 К г. n ,

P o V = n 0 K l = > P 0 = -------- —------------------------------------------- — => r n = 2 .5 atm
2 2 °2 V 2.24 L 2

nN = 3.5 ■ ■= 0 .1
. 2 5. mol p n T v P ~ 0.25 + 0.125 + 1 . 5 0, l!n , ,
2 28 g/m
g/miol r= n °2 P 'r = ----------6 ^ 2 ---------- x 2.5 = 18.75 atm
' .......
nj|e = 1.5 mol

EXER C ISE 3.28 A mixture of gases contains 6 g of He and 5 g of l-Ь gases. If the total pressure is
atm, calculate the partial pressure of l b . He:4, 11:1 l.25atm

EXERCISE 3.29 What is the partial pressure of H2 in a gas mixture containing 1 g H2, 13.2 g of C 0 2,
and 8 grams of Ar confined to a volume, of I L at 27°C'.’ What is the total pressure in the container ?
H: 1, C: 12, 4:16, Ar:40 123 a t m , 2 4. 6 at m
--------------------------
EX E R C ISE 3.30 In a container there arc 6.4 g of Cb, 0.1 mol of N 2, 1.204 x 1023 molecules of Cll.i
and some helium. He. If the total pressure in the container is 350 mmHg and the partial pressure of He is 100
mmHg, what is the mole number of He in the mixture ? Hint let the mole num ber of He be x. Then the total
mole num ber of gases will be n p , + njq^ + OCH4 + "“,l

E X A M P L E 3.28 C a l c u l a ti n g P a r t i a l P r e s s u r e
Problem : Nitrogen gas in a 10 liter container exerts I atm pressure at 27°C. When this gas is placed into a
40 liter container which already contains some oxygen gas, the pressure increases to 1.25 atm at the same tem­
perature. Calculate the partial pressure and mass of oxygen.
Solution : When the nitrogen gas is transferred from 10 liter container to 30 liter container its pressure would
be Pj x V, = P2 x V 2 => P 2 = P) x (V i/V 2) = 1 atm x (10 L/40 L) = 0.25 atm
But the pressure becomes 1.2 atm because there is some 0 2 gas initially. Then we can calculate the partial pres­
sure of 0 2 . P (>2 = 1.25 - 0.25 = 1 atm
To calculate the mass of oxygen, we have to know its mole number
*
P q ,x V ] atm x 40 l . .- .
n 0 = - — ----- = .................................. = 1.63 mol
RT 0.082 (L atm/mol K) x300 К
m o 2 = 1-63 mol x 32 g/mol = 52.2 g

EXERCISE 3.31 250 cm ! of nitrogen gas at l .00 atm, and 25CC arc transferred into a 150 c m ' container
filled with oxygen gas at l .00 atm, and 35' C. If the final temperature becomes 32 C , what will be the final pres­
sure ? 2.7 atm
88 Chapter 3

E X A M P L E 3 . 2 9 U s in g C o m b in e d G a s E q u a tio n
Problem : When the valves arc opened in the given figure and the temperature is increased to 127°C, calculate
the pressure of each gas, and the total pressure (Neglect the volume of connecting pipes).
Solution : When the valves are opened, the volume of each gas becomes 12 liters. The pressure of each gas
will be calculated as follows.
PV
Opening the valves does not change the mole number of each gas. Or пцс = п’це Recall that n = —— then
RT
PwV
1-fcV He P'rrpV'
Hev He
=> So the partial pressure of gas
R T Ifc R T ’He

He, P[[e may be found as follows.

P ii<?VHc-T'itc 9 atm x 2 L x 400 К

P ' He — 2 atm
V '„
He,T1 He 12 L x 300 К
P)te = 9 atm t=2" °C

p n 7 n J n 2 12 atm x 3 L x 400K
Sim ilarly P V 4 atm
V 'n T Nj 12 L x 300 К

And Px = P'1Ie + P'No = > P j = 2 + 4 = 6 atm.

E X A M P L E 3 . 3 0 U s in g B o y le 's L a w
Problem : When the stopcock is opened in the given figure, what will be the pressure of each gas, and the to­
tal pressure at the same temperature ? The atmospheric pressure is 750 mmHg, and assume no reaction between
the gases.
Solution : The pressure o f the gas in the first balloon
Pile = 400 mmHg. The pressure of the gas in the second bal­
loon PAr = 750 - 300 = 450 mmHg. W hen the stopcock is
opened, the gases will be mixed. In this case the volume of
each gas will be 5 liters. The pressure of each gas may be cal­
culated according to the procedure described in example 3.29.
Р цУ ш _ P'lbV'lb P 11У i t _ 400 mmHg x 2 L
P' lb - = 160 mmHg
R T Ifc R T 'ifc V Ib 5L
_ P л У A t _ 450 mmHg x 3 L
Sim ilarly P ArV Ar = P 'ArV’Ar => P ’Ar = 270 mmHg
V’Ar 5 L
And PT = 160 + 270 = 430 mmHg

EXER C ISE 3.32 When Lite valve is turned on in the given

figure, what will be the levels of mercury in each manometer at the
same temperature ?

3.4 COLLECTING GASES OVER WATER

W hen a gas is prepared in a laboratory it is frequently co llected o v er w a ­
te r if it is n o t soluble in w ater. Initially, the inverted tube is fillled com pletely
 The Gaseous State o f M atter (Kinetic Theory) 89

w ith w ater. A s the gas b u b b le s th ro u g h the w a te r to th e to p , th e w a te r is

pushed out o f the tube. T h e gas collected in this w ay is not pure. T h e collected
gas is m ix ed w ith w ater vapor. See F ig u re 3.13. T he to ta l p ressu re o f the m ix ­
ture is the sum o f the p a rtia l p ressu re o f the gas a n d the p a rtia l p ressu re o f the
w a ter va p o r (See Table 3.1)
Pi = P g a s + P w a t e r » P g a s = I*T ' P w a t e r

as you can see, eq u a tio n is an ap p lic atio n o f the eq u atio n fo r D alto n 's
P№ L aw o f p artial pressures.
TABLE 3.1 V apor P essu res o f W a te r o f V a rio u s T e m p e ra tu re s

f A
Temperature Pressure Temperature Pressure Temperature Pressure
(°C) (mmHg) (°C) (mmHg) (°C) (mmHg)
FIGURE 3.1 ЗД s a m p le
5 6.5 17 14.5 29 30.0
o f g a s that d o e s n o t rea ct
6 7.0 18 15.5 30 31.8
with w ater c a n b e co llect­
e d o v e r w ater. W h en th e 7 7.5 19 16.5 40 55.3
w a te r le v e ls a re m a d e 8 8.0 20 17.5 50 92.5
e q u a l in sid e a n d o u ts id e 9 8.6 21 18.7 60 149.4
o f th e co n ta in e r th e p r e s ­ 10 9.2 22 19.8 70 233.7
su re o f g a s in th e bo ttle is 11 9.8 23 21.1 75 289.1
th e s a m e a s th e air p r e s ­ 12 10.5 24 22.4 80 355.1
sure. H ow ever, th e p r e s ­ 13 11.2 25 23.8 85 433.6
s u r e o f th e g a s c o lle c te d 14 12.0 26 25.2 90 525.8
is fo u n d b y su b tra c tin g
15 12.8 27 26.7 95 633.9
v a p o r p r e s s u r e o f w a te r
13.6 28 28.3 100 760.0
from a tm o s p h e r ic p r e s ­ 16 J
su r e .

E X A M P L E 3.31 C o n s id e r in g V a p o r P r e ssu r e on P r e ssu r e C a lc u la tio n s

Problem : At 23°C and 760 mmHg pressure, 150 mL of 0 2 gas is collected over water. What is the volume
of the dry oxygen gas at STP ? (Рц2'0 = 21.1 mmHg at 23°C)
Solution : PT = P0 _, + Р ц 2о -> 260 mmHg = P q 2 +21. 1 mmHg -+ P q 2 = 738.9 mml l g
For the oxygen gas : P ,V , _ P 2V 2 _ P ,V ,T 2 _ 738.9 mmHg x 150 mL x 273 К ^
Pi = 738.9 mmHg P2 = 760 Tj T2 ^ 2 P 2T , 760 mmHg x 296 К
V j = 150 mL V2 = ?
T | = 296 К T 2 'p .273 К V 2= 134.5 mL

EXERCISE 3.33 50 ml. of H2 (g) were collected over water at 2 3 'C. The pressure of the gas in the gas
collecting tube is measured as 805 mmHg. Find a) the volume of dry l b gas at STP b) the mass of water vapor
in the gas collected. ( P i b o ( a ) = 21 mmHg at 2 3' С ) а ) 4 7 . 5 m L h)1. 02 т ц

EXAMPLE 3.32 U sin g V a p o r P r e ssu r e to C a lc u la te T o ta l P r e s s u r e

Problem : In a container there is some methane gas, CH4, and a little amount of liquid water at 26°C. If the
total pressure is 325 mmHg and the vapor pressure of water is 25 mmHg al this temperature, what will be the fi­
nal pressure in the container when the volume is halved ?
go Chapter 3

Solution : If there is some liquid water in the container then there will be its vapor. Because water (any liq­
uid) evaporates at any temperature. In that case the pressure in the container is the total pressure of water vapor
and the gas.
P cii 4 = Р т - Рц2о = 325 mmHg - 25 mmHg => PCh 4 = 300 mmHg
The vapor pressure o f a liquid depends on only the temperature when the vapor is in contact with its liquid. When
the volume of the container is halved at the same temperature, the vapor pressure remains the same but the pres­
sure of the gas becomes;
Pj V, 300 mmHg x V , n
PtVi = PoV2=> P 2= - ± - 4 = ----------------- -= > P 2= 6 0 0 mmHg
t 1 2 2 2 у2 V j /2

then the total pressure will be: Plotai =P gas+ P Water

Px = 600 + 25 = 625 mmHg

E X A M P L E 3 .3 3 C o n s id e r in g V a p o r P r e ssu r e on C a lc u la tio n s
Problem : W hen some N2 gas and a little amount o f liquid water are introduced into a container. The pressure
is measured to be 600 mmHg at 19°C. If the volume of the container is increased fourfold and the temperature is
increased to 23°C, what will be the total pressure in the container? P h 2Q = '6 m m Hg at 19°C, and
P h 2o = 21 mmHg at 23°C.
Solution : At 19°C Plolal = Pjsj2+ P h 2o => PN2 = 600 mmHg - 16 mmHg => P N2 = 584 mmHg
For nitrogen gas : Initially finally
р У . P 2V 2 „ P iV /r 2
P t = 584 mmHg P2 = ? - 7= - - - = r ~ 311(1 P . .. T
M *2 V2M
V. = V V2 = 4 V
0 584 mmHg x V x 296 К uem „u„
Ti = 292 К T2 = 296 К p 2= ----------- 4 у x 292----------- = ё

After the changes in volume and temperature the pressure of N2 will be 148 mmHg. The vapor pressure of water
is affected by temperature only when the liquid and its vapor are in contact. When the temperature is increased
from 19°C to 23°C", the vapor pressure vail become 21 mmHg at 23°C. Then, the final pressure in the container
is:
pT = + P ||20 = 148 + 21 = 169 mmHg

EXERCISE 3.34 A 42 mL. nitrogen gas was collected over water at IО С. The levels of water are made
equal inside and outside. The atmospheric pressure is 765 mmHg. What will be the pressure of the gas when the
gas collecting tube is pushed into the water so that the volume of the gas in the tube is half the original gas vol­
ume ? Р ц 2о = 15 mmHg I SI S штИц
 The Gaseous State o f M atter (Kinetic Theory) 91

SO M E NEW TER M S

Absolute temperature is the lowest possible Kinetic energy is the energy o f motion.
temperature which the nature admits, or that tempera­ Kinetic Theory of gases : A set o f postu­
ture at which the particles whose motion constitutes lates (assumptions) about gases used to explain the gas
heat would be at rest, being a hypothetical point 273 laws.
degrees below 0°C. M anom eter is a device used to m easure the
S ta n d a r d a tm o s p h e re is the pressure that pressure of a gas.
supports a column o f mercury 760 mm high at 0°C. Millimeter of mercury (mmHg) is unit of
Barom eter is a device used to measure at­ pressure equal to 1/760 atm, or 1 torr.
mospheric pressure. Molar volume is the volum e o f 1 mol of a
Boyle's Law : The volum e o f a given mass gas at STP. 22.4 liler/mol.
o f a gas is inversely proportional to its pressure at Mole fraction is the ratio of the num ber of
constant temperature. moles of one component o f a gas mixture to the total
Charle's Law : The volum e o f a fixed number of moles of all components.
amount of gas at constant pressure is directly propor­ Partial pressure is the pressure exerted by an
tional to the absolute (kelvin) temperature. individual gas in a mixture.
Diffusion is the escape of a gas from a con­ Pressure is a force per unit area.
tainer through a liny hole. Torr is unit of pressure equal to 1 mmHg.

R E V IE W Q U E ST IO N S

3.1 W eather balloons are partially inflated and

then released; yet, as they ascend, the balloons expand. 3.10 W hat causes the atmosphere to exert a force
Explain. on the earth ?

3.2 W hy don’t all the gas molecules in the atmos­ 3.11 Mercury has a low vapor pressure. W hat ad­
phere simply fall to earth ? vantage does this give to the use of mercury in a Torri­
celli barometer ? .
3.3 W hich postulate (s) of the kinetic theory can
be used to justify Dalton's Law of Partial Pressures ? 3.12 W hy is the high density o f mercury on ad­
vantage in a Torricelli barometer ?
3.4 W hy does the pressure build up in a tire on a
hot day ? Explain in terms of the kinetic theory. 3.13. State the pressure - volum e law in both
words and in the form o f an equation.
3.5 W hy is it desirable to express all temperatures
in Kelvins when working problems dealing with gas­ 3.14 Give the temperature - volum e law in both
es? words and in the form o f an equation.
3.6 According to the results o f the kinetic theory,
what happens to, the gas particles at 0 K, absolute 3.15 A spray can may be used until the pressure
zero? inside the can is about 1.1 atm. But it is not advised to
3.7 W hat impossible conditions would have to be throw such a used can into a fire. W hy ?
met to lower the temperature of a gas below O K ?
3.16 Which will diffuse faster under the same con­
3.8 If you cause the temperature o f a gas to rise, ditions. H 2 or O 2 ? How many times faster ?
what is actually happening to the gas particles ?
3.9 W hat is the difference between force and pres­ 3.17 W hat is an ideal gas. Under which conditions
sure ? gases behave more ideally ?
92 Chapter 3

R E V IE W PROBLEMS

3.18 In a closed-end manometer the difference be­ 3.23

tween mercury levels is 30 mm, and the atmospheric The liquid in the manome­
pressure is 760 mmHg. W hat is the pressure of the ter is glycerol (d= 1.25
gas ? 30 mmHg g /c m 3) and Patm = 0.95
3.19 A gas is gradually added to a closed - end atm. C om pute the pres­
h=16.32
manometer. Draw a figure showing each of the follow­ I cm
sure of the gas in mmHg.
ing cases. УЗ 7 mmHg
a) W ithout any gas in the manometer bulb
b) With some gas exerting 400 mmHg pressure
c) With some gas exerting 760 mmHg pressure
d) Answer the choices a, b, and с for an open-end
manometer. Assume Patm = 760 torr.

3.20
I

The volume, and temperature of O 2 and SO 2 gases

are equal.
a) Find the pressure of each gas
b) Compare the average kinetic energies of 0 2 and
S 0 2 molecules
И 'Patm =760 mmHg, determine the pressure of each c) Compare the mole numbers of the gases
gas. d) Compare the masses of the gases
3.21 a ) 9 6 0 m m H t$andjl20mmHg, d ) m o 2= 1 .5 m s o 2

3.25 A gas is heated in a closed container. Predict

the changes in the following properties of the gas
a) mass b) mol number c) density
d) pressure e) average molecular velocity

3.26 The density of solid, liquid and gaseous ni­

trogen (at STP) are 1.03 g/m L, 0.81 g/m L and
3.22 The average density of air is 0.00129 g/mL.
0.00125 g/mL respectively. Compute the molar vol­
Calculate the height of air column that exerts a pres­
ume of nitrogen for each physical state. Account for
sure of 1 atm. Assume that the density of air does not
the differences in your answers.
change with altitude. d n g = 13.6 g/mL 8012 m

G raham 's Law of Diffusion

3.27 Compare the diffusion rales of the following a) He and CH 4 b) Cb and S 0 2
pairs. c) Gas A (d = 0.09 g/L) and gas В (d = 1.44 g/L)
 The Gaseous State o f Matter (Kinetic Theory) 93

3.28 A closed container contains equal moles of a) Compute the molecular weights of the gases X
H 2, He, C H 4, S 0 2, and HI gases. The valve of the and Z. »
container-is opened for a very short lime and closed b) W here will these gases meet in tube in the given
again. Compare the relative numbers of moles of gas­ figure if the valves of the gases tire opened simultane­
es rem aining in the contanincr. H: l , H e:4, C: 16, ously ? Assume the gases are under identical condi­
S :3 2 ,1:127 п ш > п 5 о 2 >пСн 4 >пНе>пП 2 tions.

3.29 U nder the same conditions, He has a diffu­

sion rate 4 times greater than that of the gas X. What 1 о1 2 3 4 5 6 7 8 9 10 11 12 13 1415

is the molecular weight of the gas X ? He:4 a)32g! m ol,128gl m ol b)at 5

6 4g /m о I 3.34 Gi v e n
3.30 Under identical conditions of temperature and
pressure it takes 6 s for H 2 to effuse through a porous В с D E I* G II I J к 1 S 02

wall, and it takes 30s for the same volume of an un­ oc occ
known gas to effuse through the sam e porous wall.
W hat is the molecular weight o f the unknown gas? a) Where will the gases meet when the valves are
5 0g/ m о 1 turned on simultaneously ?
3.31 Under certain conditions of temperature and b) The speed of a molecule varies directly with the
pressure, 200 mL of He effused through a pinhole in square root of the absolute temperature. If the tempera­
15 seconds. How long would it take 1000 mL of S 0 2 ture of He gas were increased to 273°C and the valves
to effuse through the same pinhole ? 3 00 s were opened where would the gases meet ?
c) If the tem perature o f both gases were 273°C
3.32 A small bicycle pumb is filled with helium. where would the gases meet ?
Under constant pressure the gas is expelled in two sec­ a)I b)J c)I
onds. The same pump is filled with hydrogen bromide, 3.35
gas, HBr, at the same pressure. How long will it take A sample of He is placed in
to force out this gas ? (HBr = 81) 9 sec. an apparatus shown aside. Af­
He
ter 10 min it is found that the
; 3.33 Given pressure in the evacuated por­
T: The density of the gas X is 1.43 g/L at STP. tion is 0.18 atm. If the experim ent w ere perform ed
II. The average speed of the molecules X is twicewith HBr gas under identical conditions, what would
that of the molecules Z. be the pressure in the evacuated portion ? H Bi-81
0.04 atm

A v o g a d ro 's H y p o th e s is
3.36 A vessel which can hold 0.8 g o f 0 2 can 3.38 Under a set of conditions of temperature and
i *
hold 1.45 g of X at the same conditions. Determine pressure 32 g of CH 4 occupies a volume o f 40 liters,
the m olecular -weight of 5L. f , 58 g /r tJ Calculate the volume occupied by 64 g of S 0 2 under
the same conditions. 20 L
3.37
In the container A there 3.39 A liquid weighing 0.4 g was vaporized and
are 6 g o f He, in the В found to have a volume of 112 mL at STP. W hat is
there are 9 g of X at the the molecular weight o f that liquid ? 80 g
same conditions. What is
the m olecular w eight of 3.40 Calculate the volume o f 96 g of S 0 2 and 14
X? 30 g g of N 2 at STP. 33.6LandIl.2L
94 Chapter 3

3.41 A flask is evacuated and w eighed. Its m ass is ditions, calculate the m olecular w eight o f the unknow n
found to be 158.25 g. It is filled w ith O 2 gas at a ce r­ gas. 15.7 g/ mo l
tain tem perature and pressure and then rew eighed. Its
m ass is now 158.89 g. It is em ptied and filled w ith an 3.45 A cy lin d er w ith a m ovable but airtig h t p is­
unknow n g as u n d er the sam e c o n d itio n s an d r e ­ ton, contains som e C O 2 in 400 m L volum e. W hen 16
w eighed. Its m ass is now 160.81 g. C om pute the m o­ g o f SO 2 is added to the sam e cy lin d er at the sam e
lecular w eight o f the unknow n gas. 1 28 g / m o l tem perature the volum e increases to 1200 m L. C alcu ­
late the m ass o f C 0 2 in the cy lin d er. C = 1 2 , S=32,
3.42 U nder id e n tic al c o n d itio n s th e v o lu m e o f 0=16 5.5 g
0.73 g o f SF 6 (g) is the sam e as the volum e o f 0.4 g
vapor o f a liquid. F ind the m olecular w eight o f the un­ 3.46 T he p isto n s in th e cy lin d ers A an d В are
know n liquid. 80 g/mol m o v a b le a n d a irtig h t.
W hen the H 2 in the cy lin ­
3.43 U nder the identical conditions the density of Ag der В is tran sferred to the
gas X H 3 is 0.24 tim es that o f the gas X 2O 5 . C alculate cy lin d er A the volum e o f
M
the atom ic w eight o f the elem ent X. H = 1, 0 = 1 6 8 g He Tl the gas in the cy lin d er A
31 g/mol 1 g n2 -B triples. C alculate the m ass
- 1 H2
3.44 2 L o f a gas w ith a d ensity o f 0.09 g/L at o f N 2 present in the cylin-
STP, and 2.86 g o f an unknow n gas are m ixed. If the der A. 14 g
density o f the m ixture is 0.5 g/L under the sam e co n ­

Boyle's Law

f 3.47 C orrect the follow ing volum es from the in ­ 3 .5 2

dicated pressure to the standard pressure (A ssum e con­ <—40 cm- <—4 cm
stant temperature) G 4 cm
a) 250 L at 5 atm b) 80 L at 190 torr air I
c) 400 m L at 114 cm H g d) 350 m L at 380 m m H g Patm = 76cm H g
a)1250L b)20L c)600mL d)175L T
T
A m ercu ry p lu g is u sed to hl 4 cm
Ъ/А% If 4 .0 g o f gas at 25°C occu p ies 4 L at a trap som e air in a capillary tube i
p ressure o f 1.0 0 atm , w h at w ill b e its volum e at a as show n figure I.
pressure o f 2.50 atm at the sam e tem perature ? A s­ By erectin g or in v ertin g th e д
1П
sum e ideal behavior. 1 L6 L capillary figures II and III are obtained. C alculate the
3 .4 9 heights o f air colum n in the tube in each case.
Paim=76ernHg (1 38 c m, 42.2 cm
C a lc u la te th e v o lu m e at 3.53 An inflated balloon has a v o lu m e o f 100 L
STP of C O 2 gas in the 'at 1 atm pressure at sea level, and is allow ed to rise to
bu lb o f th e m a n o m eter. a h eig h t o f 2100 m. A ssu m in g the tem p eratu re re ­
P a,m = 7 6 c m H g h = 1 9 c m H g m ains co n stan t, w hat is the final vo lu m e o f the b a l­
1.25 L loon ? Suppose that the atm ospheric pressure decreases
3.50 A lank o f oxygen gas for m edical use c o n ­ 1 m m H g in each 10.5 m rise. 135.7 L
tains 30 L o f oxygen gas at 150 atm. W hat is the v ol­
um e o f the oxygen gas at standard pressure? 3.54 An air bubble o f 2.5 L volum e released from
4500 L a subm arine 173 m below the sea level rises to the sea
3.51 An airtig h t cy lin d er contains 8 g o f H 2 in a surface. W hat is the final volum e o f the air bubble?
volum e o f 10 L. W hat is the density o f the H 2 after d s e a w ater = 1-1 g/m L d Hg = 13.6 g /m L , P atm = 7 6
the pressure is halved at constant tem perature ? cm H g. A ssum e the tem perature rem ains constant.
0.4 g/L •T* 48.53 L
 The Gaseous State of M atter (Kinetic Theory) 95

Charle's and Gay L u s s a c ’s Laws

3.55 The volume o f a gas in a gas thermometer is atm pressure. W hen it is heated from 7°C to 27°C,
50 mL at 77°C. W hat is the tem perature when the what will be the last pressure ? (Assume constant vol­
volume is 28.6 mL. Assume that the pressure remains ume) 5.4 atm
co n sta n t. -73°C

у 3.61 A pressure vessel contains 9 kg of 0 2 at 120

3.56 A gas w hose volum e is 450 mL is heated atm. If the temperature is kept constant, calculate the
from -23°C to 227°C at constant pressure. W hat is its amount of 0 2 removed from the vessel to drop the
final volume ? 900 mL pressure to 40 atm. 6 kg

3.57 It is desired to increase the volume of a gas 3.62 A container is filled with a gas to a pressure
at 27°C by 40%. W hat should be its final temperature. of 2 atm at 27°C. a) W hat pressure will be exerted in­
Assume constant pressure. 147°C side the sealed container if it is heated to 57°C ? b) At
what temperature would the pressure be 3 atm ? c) At
3.58 A gas has a volum e o f 50 liters at 77°C. what temperature would the pressure be 4 atm?
W hat would be the volum e at -73°C assuming con­ a) 2.2 atm b)177°C c)327°C
stant pressure ? 28.6 L 3.63
The gas in the bulb of the
3.59 4 gram s o f a gas occupies 1.50 liters at p atm= 7 6 0 m m H S manometer is heated from
"T
17°C and 0.5 atm pressure. W hat will be the volume 27°C to 57°C. W hat will
of this sample if the g&s is heated to 27°C with the be the difference between
h= 140 mmHg
pressure staying constant ? 1. 55 L mercury levels in the arms
of the U tube?
3.60 A sample gas in a sealed container exerts 5.0 230 mm

C om bin ed Gas Law

3.64 Correct the volumes of the following gases 3.68 A 56 ml. bubble 5 m below the sea level,''
as indicated, a) 100 L at 1 atm and 27°C to STP where the pressure and temperature are 114 cmHg and
b) 460 mL at 380 mmHg and 37°C to STP 7°C, rises to the water's surface, where the pressure is
c) 380 mL at 190 torr and 127°C to 27°C and 1 atm 76 cmHg and temperature is 27°C. W hat is the vol­
d) 960m3 at 77°C and 1 atm to 17°C and 1900 torr ume of the bubble at earth's surface? 90 m L
a) 91 L d)318.2 m3 3.69 A sealed m etal container has enough C 0 2
3.65 A sample of oxygen occupies 200 mL under that exerts 1 atm pressure at 17°C. When the tempera­
a pressure of 1140 mmHg at a temperature of 127°C. ture of the container is increased to 162°C, the volume
What volume will it occupy under standard conditions? of the container increases by 20 %. W hat will be the
204.75 mL final pressure inside the container? 1.25 at m
3.66 A gas has a volume of 152 mL at 15°C and
under a pressure of 72 cmHg. Correct the volume to 3.70 A cylinder with a movable piston contains
standard conditions. 136.5 mL 7.5 L gas at 1.8 atm and 27°C. W hen the piston is
pushed down until the volume becomes 6 L, the pres­
3.67 A fixed am ount o f a gas has a volume of sure of the gas is measured to be 3.15 atm. Calculate
6 L at 27°C and 1 atm. W hat is the volume of this the final temperature of the gas in the cylinder.
gas at 127°C and 2 atm ? 4 L 1 4 7 °С
96 Chapter 3

3/^1 A gas filled balloon having a volum e of volume at 27°C is decreased by 40.0 % ? 8 7 °c
2.73 L at STP is allowed to rise to the stratosphere, * 3 .7 4
where the temperature and pressure are -23°C and 3.8 I II
torr respectively. Calculate the final volume of the
balloon. 500 L ‘ 50 cm —> f 150 cm —>
piston
*3.72 A m eteorological balloon was designed to
have a radius of 10 m at 20 mmHg and -73°C in the
stratosphere. How many liters of He gas must be put
An airtight and movable piston is made from an in­
into the balloon at the earth's surface where the pres­
sulating material and separates the gas at 27°C in a
sure and temperature are 750 mmHg and 27°C respec­
steel cylinder into two parts as shown in the given fig­
tively? 1 . 6 8 xlO SL
ure.When the temperature o f the gas in the first por­
tion is increased to 77°C, in which direction will the
3.73 To what temperature must a sample of heli­
piston move? How many cm ?
um gas be heated to double its pressure if its initial
6 cm toward II

Ideal G as Equation
3.75 Calculate the num ber of moles o f each of b) 2.5 g/L at 730 torr and 27°C.
the following gases. c) 1400 mg/L at 152 cmHg and 77°C.
a) 164 L of O 2 at 1.5 atm and 27°C d) 1.96 g/L at STP.
b) 62 L of N 2 at 100 cmHg and -73°C a)44g/m olb)64g/m olc)20g/m old)44g/m ol
c) 820 mL of N 0 2 at 380 torr and 227°C 3.80 Compute the density of
d) 36 L of NH 3 at 1140 mmHg and 57°C a) S 0 2 at 2.45 atm and 97°C
e) 13.44 L S 0 2 at STP. b) NO at 950 mmHg and 27°C
a)10, b) 5, c)0.01, d)2 e)0.6 c) 0 2 at 700 torr and -23°C
3.76 Calculate the pressure exerted by d) C 2H 4 at STP
S t) 16 g of He in 16.4 L container at -73°C a)5.2g/L b)1.52g/L c)1.44g/L d)1.25g/L
T>) 10 g of HF in a 5 L container at -48°C 3.81 Assuming a gas behaves ideally. How many
]c) 104 g of SO 3 in a 16 L container at 27°C molecules per cubic centimeter will it contain at -23°C
xt) 6 g of NO in a 3.3 L container at 30°C and 608 mmHg ? 2 .3 5 x 1 0 ^ m olecules
a)4atm b ) l ,84atm c)2atm d)1.5atm
3.82 A gas has a density o f 3.17 g per liter at
3.77 W hat is the volume of
STP. Calculate its density when subjected to 4 atm
a) 11 g C 0 2 at 27°C and 228 mmHg
pressure at constant temperature. 12. 6 8 g/L
lb) 3.Q lxl0 23 atoms of He at 37°C and 950 torr
\ ) 2.9 g C 4H , 0 at 77°C and 2 atm. 3.83 A quantity of SO 3 occupies a volume of 1
a)20.5 L b)10.2 L c)0.72 L L at 27°C and 1 atm. The gas expands to a volume of
3.78 Find the molecular weight of the gas whose 3 L as a result of change in both temperature and pres­
a) 2.7 L at 1.2 atm and 87°C is 8.8 g. sure. Find the density of the gas at these new condi­
2.5 L at 152 cmHg and 32°C is 14.2 g. tions. 1. 08 g/ L
500 mL at 380 mmHg and -23°C is 1 g.
*3.84 A gas cylinder contains 512 g of oxygen
. 315 mL at 950 torr and 100°C is 0.80 g.
gas at 30.0 atm pressure and 27°C. How many g of
a)80 b)71 c)82 d)62
oxygen would escape if first the cylinder were heated to
3.79 Find the molecular weight of the gas whose
127°C and then the valve held open until the gas pres­
density is
sure decreased to 12.5 atm, the tem perature being
a) 2.2 g/L at 1.64 aim and 127°C.
m aintained at 127°C? 352 g
 The Gaseous State o f Matter (Kinetic Theory) 97
\ — ■

3/85 W hat percent of a sample of oxygen must be 3.91 A steel container o f volum e 49.2 L can
allowed to escape if its temperature, pressure and vol­ withstand a pressure up to 100 atm at 27°C. Find the
ume are changed from 227°C, 2 atm and 2.0 L to mass o f He that can be stored in this container at
127°C, 4 atm and 0.6 L respectively ? 25% 27°C . 800 g

3.92 In an oxyacetylene torch, the oxygen gas is

3.86 How many liters o f oxygen gas at STP con­
supplied from steel tanks containing O 2 gas under very
tain the same num ber o f oxygen m olecules as the
high pressures.In a welding process, the pressure of O 2
number of hydrogen molecules present in 25 L of H 2
gas in a 15 L tank reduced to 174 atm from 181 atm at
gas at 0.85 atm and 35°C? 18. 8 L
25°C.How many grams of O 2 had been used up?
137.5 g
3.87 An evacuated container o f 4.1 L volume
*3.93 The density o f a mixture o f HF and NO
weighs 104.0 g. When some N 2 (g) at a pressure of
gases is 1.4 g/L at 127°C and 1.64 atm. Calculate the
7.5 atm is placed into the container it becomes 125.0
mass percentage of HF in the mixture. 14.3%
g. W hat is the temperature of the gas in the container?
2 2 7 °C 3.94 A gas has the following percentage com posi­
3.88 A 10 L container holds 9.8 g of a gas at 75 tion. 15.5 % C, and 23 % Cl, and 61.5 % F. 2.65
cmHg and 50°C. W hat pressure will 12 g of the same gram of the same gas occupies a volume of 428 mL at
gas exert in a 4 L container at 0°C? 2. 55 at m 24.3°C and 742.3 mmHg. Determine the molecular
formula of the compound.C:12,Cl:35.5,F:19 C 2 CIF 5
3.89 A 31 g m ixture of C 0 2 and CH 4 gases in
24.6 L vessel at 27°C exerts a pressure of 1.5 atm. 3.95 A gas has a density of 1.01 g/L at 380 torr
What is mole number of CH 4 in the mixture ? and 77°C, and is made of 82.8 % C, and 17.2 % H by
1.25 mol mass. W hat is its molecular formula ? C4 H 10

3.96 A gaseous com pound made from В and F

3.90 Under the conditions o f 780 torr and 27°C,
elem ents is 16.2 % В by mass. 6.8 g of the same
the density of the gas X is 1.25 times the density of
com pound has a volum e of 2 L at 0.82 atm and
the propane gas, СзН 8 at STP. Determine the molecu­
127°C. Determine the empirical and the molecular for­
lar weight o f the gas X ? 59 g /mol
mula of the compound. B = l l , F=19 B F 3 , H2I76

Partial P re ss u re

3.97 A 2.46 L flask at 27°C contains 3.£ g of N 2 3.100 The mixture of 1 mol of H 2 and 56 g of X
(g)„ 0.25 mol of O 2 (g), and 9 .0 3 x l0 23 atoms of He gases exerts 3 atm. If the pressure o f X is 2 atm, what
(g). Calculate (a) the partial pressure of each gas (b) is the molecular weight of X ? 28 g / m o l
the total pressure (c) when 7 grams of N 2 is added to
the container what will be your answers to (a) and (b) 3.101 A 4.92 L container at 27°C contains 1.5 g
a ) P f l 2=1.25atm, P q 2=2.5atm b)18.75atm of C 2H 6 and a quantity of the gas X. The pressure in
c ) P j = 2 1 .25 atm the continer is 2 atm. (a) Find the partial pressure of
3.98 A gas m ixture contains 1.5 mol o f N 2, 0.5 C 2H 6 (b) W hat is the mole percentage o f X in the
mol of O 2 and 0.5 mol of CH 4 gases. The total -pres­ mixture? ' 0.25 atm, 87.5%
sure is 2 atm. Calculate the partial pressure o f each
gas. 1>N2 = 1 . 2 , P 0 2 = 0 . 4 , P e n 4 = 0 -4 . a t m 3.102 A 2.46 L flask at 27°C contains equal
3.99 In a container there is 0.5 mol o f He at 2 masses of O 2 and SO 2 gases at a pressure of 6 atm.
atm pressure. If 24 g of CH 4 are added into the com Find (a) the partial pressures of the gases (b) the mass
lainer, what will be the pressure ? 8 atm of one of the gases. a)4 atm,2 atm b)12.8 g

?
I
 *3.103 А 1.75 mol m ixture com posed o f equal 3.109
masses of CH4, 0 2 and S 0 2 gases exerts a pressure of If valve is turned on what
3990 mmHg at 27°C'in a container. Calculate (a) the will be the pressure of
partial pressures of the gases (b) the mass of one of each gas and the total
the gases (c) the volume of the container. pressure ?
a ) P C I l 4 = 2 2 8 0 , P o 2= 1 1 4 0 , P SO 2=570 b)16 g 0 . 8, 0. 6, 1. 4 atm
c)8.2 L 3 .1 1 0

3.104 A flask at 27°C contains a 12 g mixture of

P= 2 atm P= 5 atm
He and H 2 gases at a pressure o f 2.5 atm. The partial
pressure o f He gas is 38 cmHg. Calculate (a) the par­ By pushing the pistons the gases are filled into the
tial pressure of H 2 (b) the number of moles of each 4 L container. W hat will be the pressure of the mix­
%as (c) the volume of the container. ture? Assume constant temperature. 4 at m
a)2atm b)lmol He, 4m olH2 c )49.2 L
J
3.111 11 g o f dry ice (C 0 2) is dropped into a
*3.105 The pressure of a mixture of gases is 825 bottle of 0.75 L volume at an initial air pressure of 1
mmHg. The mixture consists of 20 % He ? 32 % 0 2, atm and temperature of 30°C. The bottle is sealed and
32 % CH4, and 16 % S 0 2 by volume. Calculate (a) the C 0 2 is allowed to evaporate. W hat will be the ul­
the partial pressure of each gas (b) if the composition timate pressure in the bottle at the same temperature ?
of the mixture were by mass instead of volume, what 9.28 atm
would be the partial pressures of gases.
a)P lie-165 mmHg P c i l 4~ 2 6 4 m m H g
b ) P j i e=5 0 0 m m H g P g Q 2= 2 5 m m H g

*3.106 A gaseous compound Y contains 85.7 %

С and 14.3 % H by mass. Equal masses of Y and CH 4
mixture exert a total pressure of 1450 mmHg. If the
partial pressure of CH 4 is 1050 mmHg, what is the
molecular formula of Y ? C 2 H^ When the valves M and N are opened (a) what will
be the partial pressure o f each gas and the total pres­
3.107 A mixture of C 0 2 and 0 2 molecules exerts sure (Assume constant temperature) (b) draw a new
538 mmHg pressure at a constant temperature. figure representing the final situation of the gases.
I. The partial pressure of C 0 2 is 500 mmHg in the
mixture
II. The oxygen in the m ixture occupies a volume
о
of 2cm at 1 atm at the same temperature.
W hat is the initial volume of the mixture in cubic
centim eter? 40

3.108 The oxygen gas in a 40 L container at 700 The gases А, В, С arc at the same temperature and
mmHg at 77°C and the hydrogen gas in a 20 L con­ do not react with one another. Calculate the pressure'
tainer at 600 mmHg at 27°C are pumped into a 30 L in the 5 L container and the partial pressure of gases in
container at 57°C. W hat will be the final pressure in the mixture formed by opening the valve (s)
the container at 57°C ? 1320 m m H g (a) only M (b) M and N together
(c) N and О together (M closed) (d) M, N, and О
( a ) P д =1 atrrfy' ( b ) P д = 0 . 6 7 a t m d ) P д =0.5 8 atm
 The Gaseous State o f Matter (Kinetic Theory) 99

C ollecting G ases Over W ater

3 .114 50 mL of H 2 gas are collected over water at higher than the level of water outside. If the volume of
23°C and 741.1 mmHg total pressure. W hat is the the vapor is 1.23 L and the atmospheric pressure is
volume of this gas at STP? (Ph2o=21.1 torr) 788 mmHg, compute the molecular weight of the liq­
43.7 mL uid. Pii2o=27mmHg, dIl2o= lg/m L, dHg=13.6 g/mL
3.115 W hat volume of "wet" methane gas would 1 64 g/ m ol
you have to collect at 15°C and at 763 mmHg, if you 3.119 If 100 mL o f a dry gas at 20°C and 750
needed 250 mL o f dry methane gtjs at STP. m mHg is collected over w ater at 25°C and 750
Pl-I2o=13m m H g at 15°C. 267 . 3 m L mmHg, the volume becomes 105 mL. W hat is the va­
por pressure of water at 25°C ? 23.53 m m H g
3.116 A 42 mL sample of hydrogen was collected
over water at 25°C and a total pressure o f 744 torr. *3.120 A mixture of 4 g of Ar and 6.4 g of 0 2
Calculatc its partial pressure in torr. W hat is the vol­ gases are put into a 8.2 L container which already has
ume of dry hydrogen gas at 1110 torr and 17°C ? some chloroform (CHCI 3) at 27°C. After a while the
Р ц 2о at 25°C = 2 4 m m H g 2 6. 5 mL pressure in the container is found to be 803 mmHg at
the same temperature (a) calculate the vapor pressure of
*3.117 A sample of air is collected over water at the chloroform at 27°C (b) calculate the num ber of
20°C. At equilibrium the total pressure of the moist chloroform molecules in the vapor phase.
air is 1 atm. The mole percentage composition of dry a) 1 1 9 m m H g b ) 3 . 1 4 x l j 0 22
air is 78 % N 2, 21 % 0 2, and 1 % Ar. Calculate the *3.121 Some helium gas taken from a steel tank
partial pressure of nitrogen, oxygen, and argon in the containing helium at 5 atm was collected over water at
wet mixture. (Ph2o=17.54 torr) 23°C. When the levels of water inside and outside the
l‘ N 2 =0.762, P a 2= 0 .2 05 , PA r=0.00977 atm gas collecting vessel are equalized, the volume of He is
measured as 2.5 L. If the/pressure in the storage tank
*3.118 A 8 grams sample of a volatile/liquid is dropped to 4.95 atm after the ijemoval of the helium
vaporized and its vapor is collected over water at 27°C. gas, calculate the volume of the gas storage tank. As­
The level o f water in the gas collecting tube 27.2 cm sume Patm=1.032 atm and Ph2o=0-032 atm 50 L

M is c e lla n e o u s P ro b le m s
puncturing a pinhole in the separator, it is found that
A container has 2 g of He and the partial pressure of CH 4 in the evacuated portion is
32 g of S 0 2 at a total pres­ 2 times that of X. Find the molecular weight of X.
sure of 1000 inmHg. If the 64 g/mol
valve of the container is 3.124 Predict the gas which behaves more ideally
opened for a short tim e -in under the conditions indicated.
vacuum and closed again the pressure of the gases in (a) He at STP (b) He at 1 atm 100°C
the container drops to 500 mmHg. Assuming the tem­ (c) He at 200°C and 1 atm
perature rem ains constant, find the mass of S 0 2 re­ (d) He at 200°C and 2 atm
maining in the container. 25 . 6 g (e) C 0 2 at 200°C and 2 atm (c)

3.123 m ixture o f equal m oles of *3.125 The vapor pressures of liquids A and В are
CH 4 and X gases is placed 58.4 mmHg and 73.6 mmHg at 37°C respectively. If
CH,J
in th& apparatus shown 0.20 mol of A vapor and 0.50 mol of В vapor were in­
and vacuum
aside. ! 5 m inutes later troduced into a 100 L evacuated container at 37°C,
X

*
100 Chapter 3

what would be the total pressure in the container at change has been made. 20 m m H g
liquid-vapor equilibrium ? 112 m m H g

3.127 A 4.92 L container contains nitrogen gas at

*3.126 A cylinder with a movable piston holds 27°C and 2 atm pressure. If the nitrogen gas is intro­
some nitrogen gas and a negligible quantity o f liquid duced into a 20 L container that already contains oxy­
water at a total pressure of 450 mmHg. When the pis­ gen gas the pressure becomes 1.968 atm at the same
ton is pushed down until the volume is halved, the temperature. W hat is the pressure and mass of oxygen
pressure inside the cylinder becomes 880 mmHg. Find in the container ?
the vapor pressure of the water at the temperature the 1 .4 7 6 a tm , 3 8 .4 g

SELF TEST
1. Which one of the following does not affect the A) Adding 8 g of CH4 at 20°C
pressure of a gas ? B) Halving the volume at 20°C
A) Number of molecules C) Increasing the temperature to 40°C
B) Temperature D) Adding 16 g of 0 2 at 20°C
C) Speed of the gas molecules E) Adding З.01х1023 ССЬ molecules at 20°C
D) Numbers of atoms in the gas molecule
E) Volume of the container 6. At a certain temperature and pressure 45 g of
C 2H 6 occupy 30 L. At the same conditions 132 g of
2. W hich one o f the follow ing is the same for CO 2 occupy how many liters ? C=12, 0= 16, H=1
gases in a mixture at a definite temperature ? A) 30 B) 45 C) 60 D) 175 E) 190
A) Average kinetic energies B) Average speeds
C) Partial pressures D) Number of moles 7. 2 mol of a gas exert 1 atm pressure at 127°C in
E) Number of molecules a closed container. To make the pressure 6 atm at
27°C how many moles of gas must be added ?
A) 6 B) 8 C) 10 D) 14 E) 16

W hat is the m olecular

weight of the gas X in the
manometer ?
A) 28 B) 38 C) 44
W hat are the pressures of gases A and В in mmHg D) 64 E) 76
respectively ?
A) 900-1200 B) 800-600 C) 900-600 9. 1 g hydrogen gas in ,a closed container exerts a
D) 620-920 E) 760-460 pressure of P. If 2 g of hydrogen are added and the vol­
. 4. 2 L of SO 2 gas are expelled in 8 seconds and 2 ume of the container is doubled, what will be the final
L of X gas are expelled through a tiny hole in 9 sec­ pressure at the same temperature ?
onds at the same pressure and temperature. What is the A) 3P/2 B) 2P/3- C) P/2 D) 5P/3 E) P
molecular weight of X ? (’SC>2=64)
A) 81 B) 72 C) 64 D) 57 E) 50 10. Equal volumes of X 2 and YX 5 gases weigh
14.2 g and 41.7 respectively at the same conditions.
5. In a container there are 16 g of O 2 at 20°C at What
a is the molecular weight of X 2? (Y=31)
certain pressure. W hich one of the following dosen't A) 71 B) 80 C) 122.5 D) 142.3 E) 208.5
increase the pressure iwice ?
 \ The Gaseous State o f Matter (Kinetic Theory) 101

11. There are 5.6 g of N 2, 0.1 mol of O 2 and 2.2 17.

g of CO 2 in an 11.2 L container at 273°C. W hat is
the total pressure in atm in the container ? N 2= 28 ,
C 0 2=44, 0 2=32
A) 1.4 B) 0.7 C) 0.35 D) 3.5 E) 7

12. 4.8 g of CH 4 gas exerts 600 mmHg pressure

in a closed container; If 4.8 g of XO 3 gas are added
into the container the pressure becom es 720 mmHg
pressure. W hat is the atomic weight of X ? C :12, 0 :1 6
A liquid has an empirical formula of CH. The pres­
A) 16 B) 24 C) 32 D) 48 E) 64
sure versus the reciprocal of volume related to 19.5 g
vapor of the liquid at 127°C is given in the graph.
13. A gas has a volume of 760 mL at 127°C and
Find the molecular formula of the liquid.C= 12
800 torr. W hich is the volum e in mL of the gas at
A) C 2H 2 В) C 3H 3 С) C 4H 4
STP ?
A) 423 . # 5 4 6 C) 612 D) 652 E) 720
D ) C 5H 5 0 C 6H 6

18. N 2 gas was collected over water at 25°C. The

14. A container is full of N 2 gas at a pressure of
pressure in the container was found to be 420 mmHg.
1200 mmHg. When a quantity of N 2 that exerts a
What would be the pressure when volume is halved at
pressure of 400 mmHg in 3 L container is removed
25°C? (PH20=24mmHg)
from the container, the pressure decreases to 1000
A) 214 B) 238 C) 396 D ) 816 E) 840
mmHg from 1200 mmHg. W hat is the volume of the
container ? 19. In a mixture of equal masses of CH 4 and O 2
A) 2 L B) 3 L C) 4 L D) 5 L E) 6 L gases, the partial pressure of CH 4 is 100 mmHg. W hat
is the total pressure of the mixture in mmHg ?
15. The density of O 2 at 3 atm and 207°C is the A) 50 В) 10O C) 150 D ) 200 E) 300
same as the density of ihe gas X at 1 atm and 127°C. 20. There are equal masses of 0 2 and CH 4 gases at
W hich is the gas X ? H= l , N =14, 0 = 1 6 , S=32, the same temperature in two different containers with
C l= 35.5,1=127 equal volume. W hich one o f the following is COR­
A) HI B) N 0 2 C) Cl 2 D) S 0 3 E) N 20 5 RECT ? C H 4 =16 О 2 =32
A) The pressures of the gases are equal.
16. When the valve is opened, the final pressure B) The kinetic energies of 0 2 molecules are greater.
becomes 50 mmHg. W hat C) The average speeds of 0 2 and CH 4 molecules
is the value of x ? tire equal.
A) 2 B) 2.5 C) 3 D ) CH 4 gas has more molecules.
D) 4 E) 6 E) The avarage speed of CH 4 molecules is 2 times
greater than 0 2 molecules.
 CHAPTER
Chemical Reactions

The objectives of this chapter are to enable the student

to :
1. Identify physical and chemical changes.
2. Define the exothermic, and endothermic reactions.
3. Define a chemical reaction in terms of reactants and
p ro d u cts.
4. Write equations for chemical reactions.
5. Balance some equations by inspection.
6. Define the types of chemical reactions.
7. Perform calculations about chemical equations con­
c e rn in g ,
a) quantities of reactants and products
b) limiting reagent
c) impure substances
d) consecutive reactions
e) simultaneous reactions
f) determination of atomic weight
g) determination of empirical formula
 Chemical Reactions 105

4.1 PHYSICAL AND CHEMICAL CHANGES

O ne o f the basic goals o f ch em istry is to p ro v id e som e k n o w led g e w ith
w h ic h w e c a n u n d erstan d the w orld around us. T h ere are b illio n s o f b illio n s
k in d s o f c h an g es ta k in g p lace around us. T o u n d ersta n d the n atu re o f th ese
changes, th ey m u st b e sy stem atically investigated. S cientists h av e do n e these
in v estig atio n s and classified the chan g es in m a tte r into tw o groups. 1 . p h y si­
cal ch anges 2 . chem ical changes.
4 .1 .1 PH Y SIC A L C H A N G E S

A p h y sic al c h an g e is a c tu ­ S u b ta n c e s are alw a y s u n d e rg o in g ch an g es. P h y s ic a l c h a n g e s a r e

ally a c h an g e in the p h y s ­ changes in the condition or state o f a substance. P h y sical changes d o n 't result
ical p ro p e rty o f m a tte r in th e fo rm atio n o f new substances. A n ex a m p le o f a p h y sical c h an g e w ould
su c h as c o lo r, d en sity ,
be the m e ltin g o f ice, so lid form o f w ater. I f a sam p le o f ice is h eate d , it
s t a te ....
A p h y sic al p ro p e rty o f
changes into liquid form o f w ater at 0°C. B ut there is no change in the c o m p o ­
m atter can be m ea su re d or sitio n o f w ater. T h e b o iling o f w ater also involves a ph y sical change from the
o b serv ed w ith o u t chang'- liq u id to th e g aseo u s state, b u t the c o m p o sitio n o f w a ter is still u n changed.
ing th e c o m p o s itio n o f S ee F ig u re 4.1.
m a tte r. heating heating
>
ICE WATER WATER VAPO R
cooling ' cooling
FIGURE 4.1 Phase changes of water
A sm all quantity o f energy accom panies the process o f physical changes.
F o r ex am p le 1.44 kcal o f h eat is n eed ed to m elt 1 m ol o f ice. W h en the te m ­
W a t e r c o n t a i n i n g H 2S 0 ;
peratu re is raised to 100°C at 1 atm , w ater begins to boil. T h e en erg y added to
th e liquid w ater during boiling causes the m olecules to separate from each o th ­
er. 9.72 k cal o f h eat is required to ch an g e 1 m o l o f liq u id w a te r to g aseo u s
Oxygen (10 m l)
state
4 .1 .2 C H EM IC A L C H A N G E S
H y d r o g e n (2 0 m l)

The changes in w hich new substances are p ro d u c e d are ca lled ch e m ic a l

P o s it iv e e l e c t r o d e '
c h a n g e s o r c h e m ic a l r e a c tio n s . In a c h em ic al re ac tio n th e id e n tity o f the
N e g a tiv e e le c tro d e
starting m aterials are com pletely different from the m aterials produced. C hem i­
cal ch anges p ro d u ce am azing changes in the p ro p erties o f the starting m a te ri­
als. F o r ex am ple, if the iron filings are exposed to m oisture, ho w ev er, the iro n
w ill soon be changed into rust. T h e p ro p erties o f ru st are d iffe re n t from those
o f iron and oxygen and it is concluded that a new substance has been form ed.
W e can d e co m p o se th e w a te r in a so lu tio n o f w ate r and su lfu ric acid
p assin g an electric cu rren t th ro u g h the solution. T h e w ay to do th is is sh o w n
in F ig u re 4.2. I f one m o le o f w ater has d eco m p o sed , one m o le o f h y d ro g e n
and one- h a lf m ole o f oxy g en gas are p roduced. E lectric al en erg y cau ses the
FIGURE 4 . ^Decom posi­ d ecom p o sitio n o f water. I f energy is ab so rb ed in a chem ical reaction, it is sa id
tion of the wa ter into the to be a n e n d o th e r m ic r e a c tio n . T h e e n e rg y re q u ire d to d e c o m p o se one
elements; hydrcqen and ox­ m o le o f w a te r is 68.3 kcal.
ygen. Water has .totally dif­
ferent properties tt'?an those
2H 20 + energy - a 2H 2 + 0 2
of hydrogen and oxy:qen T h e ch em ical ch an g e in the fo rm atio n o f w a te r is ex actly the rev erse o f
106 Chapter 4

th e ch em ical change in the d ecom position o f w ater. T o m ake one m ole o f w a­

ter, one m o le o f h ydrogen and o n e -h a lf m o le o f oxy g en react w ith each other.
T w o m oles o f h y d ro g en react w ith one m o le o f oxygen, to form tw o m oles o f
w ater and 2x68.3 kcal o f h eat energy is released. A chem ical reaction in w hich
en erg y is re le a se d is ca lled an ex o th erm ic rea ctio n . See F igure 4.3 to c o m ­
pare th e decom position and form ation o f water.

m +
Н2 H2
02

о20 Q2 + ” — C02D + ф2
^I ~п <
UJ СИ H Щ

л FIGURE 4.3 Formation and decomposition of water

E X A M P L E 4.1 I d e n tify in g P h y sic a l a n d C h e m ic a l C h a n g e s
Problem : Identify each of the following as a physical or chemical change.
a) hard-boiling an egg b) magnetizing iron c) breaking bread into pieces
d) digestion of food e) dissolving sugar in water 0 souring milk.

Solution : a, d, f are chemical changes, b, c, e are physical changes.

E X A M P L E 4.2 R e la tio n s h ip M o le s a n d H e a t R e le a se d
Problem : Given N 2 (g) + 2 O 2 (g) + 16.2 kcal —> 2 NO 2 (g) Is this reaction endothermic or exothermic ?
Solution : The reaction is endothermic. Because 16.2 kcal o f heat energy a~e absorbed by the reactants to give
products.

EXER C ISE 4.1 Given the reaction I/ 2N 2 (g) + З/2 Н 2 (g) -» NH 3 (g) + 11.0 kcal. Is this reaction exo­
thermic or endothermic ?
In c h e m ic a l r e a c tio n s :
a) M a ss is c o n se r v e d : T h e m ass o f th e re a c ta n ts is e q u a l to the
m ass o f the products.
2 H 2O —> 2 H 2 + O 2
36 g = 4 g + 32 g
b) A to m s a re co n ser v ed : T h e to ta l n u m b e r o f ato m s o f e a c h ty p e
rem ains u n ch an g ed in a chem ical reaction. A tom s can n eith e r b e created nor
destroyed in a chem ical reaction.
2H 20 -> 2 H 2 + 0 2
4 H atom s < - > 4 H atom s
2 О atom s <->2 0 atom s
c) T h e ch e m ic a l b o n d in g c h a n g e s : T h e a rra n g e m en t o f atom s is
different in the reactants from w h at it is in the products o f a chem ical equation.
2 H - О - H -> 2 H - H + О = О
d) T h e n u m b e r o f m o le s, m o le c u le s, and v o lu m e o f th e su b sta n ces
 Chemical Reactions 107

m ay not be conserved in chem ical reactions.

e) T h e e le c tr ic a l c h a rg e is c o n se r v e d : T he total charge o f reac­
tants m ust be the same as that o f products. (W e w ill see the application o f this
rule later.)
/4 .2 CHEMICAL EQUATIONS
W e have seen that w e m ay represent pure chem ical substances by sym ­
bols or formulas. W e m ay use these sym bols o f form ulas to represent chem i­
A chem ical e q u atio n does cal reactions. The representation o f a chem ical reaction is important for the
n o t give any d e ta il about chem ists all over the world to com m unicate w ith one another about chem ical
- how it occurs reactions. Therefore a standard w ay to represent chem ical reactions has been
- how fa st it is
developed.
- how long it tak es to go
c o m p le tio n 4.2.1 W R IT IN G C H E M IC A L E Q U A T IO N S
A c h em ica l rea ctio n is a p ro c e ss in w hich new c h e m ic a l su b sta n ce s ,
c a lle d p ro d u cts are p ro d u c e d fr o m a se t o f o rig in a l su b sta n ces, ca lle d rea c­
C h e m ists g e n e ra lly in d i­
c ate the p h y sic a l sta te o f
tan ts. A sym bolic representation o f a chem ical reaction is called a ch em ical
the reactan ts and p ro d u c ts eq u a tio n . In a chem ical equation the formulas o f the reactants are written on
by u sin g the letters g, 1, s the left side and those o f the products, on the right. The tw o sides are joined
o r aq in p a re n th e se s to by an arrow ( —> ).
show gas, liq u id , solid,
In w r itin g a ch e m ic a l e q u a tio n
and the aq u eo u s solu tio n .
2 H 20(1) —» 2H 2 (g) + 0 2(g)
a) W e h a ve to kn o w w h a t the rea cta n ts a n d p ro d u c ts are. A t this stage
you are not expected to predict the products o f a reaction. Later on you w ill
gain experience to be able to make intelligent guesses.
b) W e have to w rite the c o rrec t m o le c u la r fo r m u la f o r each re a c ta n t
a n d each product.
c) W e m u st show that atom s are conserved.
T hese three steps are illustrated in the follow ing exam ple.W hen propane
gas bum s com pletely, the products are carbon dioxide and water. Let us write
an equation to represent this combustion reaction.
Propane + O xygen —> Carbon dioxide + Water (w o rd equation)
C 3H 8 + 02 —> C 02 + H20 (skeleton equation)
This equation should be balanced to satisfy the conservation o f atoms.

4.2.2 B A L A N C IN G C H E M IC A L E Q U A T IO N S
T o be valid an equation m u st conserve atom s. In o ther w ords the n u m b er
o f ato m s o f each kind on both sides o f the arrow m u st be the sam e. T o do this
a suitable set o f coefficients are placed in front o f the form ula o f each o f the re­
actan ts and products. T h e pro cess o f fin d in g th ese co e ffic ien ts is c alled b a l­
a n c in g e q u a tio n .
C o n sid er the burning reaction o f propane described in section 4.2.1.
СзН 8 + 0 2 —> C 0 2 + H 20 (skeleton equation)
A u se fu l first step in b alan cin g any e q u atio n is to ch o o se the c o e fficien t
o f the su b stance th at contains the la rg e st n u m b e r o f atom s p e r m o lec u le as 1,
108 Chapter 4

and ad ju st th e o th e r co efficien ts acco rd in g to the c o e fficien t ch o se n as 1. In

o u r exam p le th e m ost com plex substance is C 3H 8 (11 atom s p er m olecule). So
w e ch o o se its co efficien t 1. B ut the co efficien t one is n o t show n in the eq u a­
tion.
1C3H 8 + O 2 —> CO 2 + H 2O
N e x t ste p is to lo o k fo r th e elem e n t (s) in the m o st co m p lex su b stan ce
th a t ap p ears o n ly o n ce on each side o f the eq u atio n , and to b ala n ce the n u m ­
bers o f this elem ent o r these elem ents. H ere all tw o elem ents (C and H) appear
o n ly o n ce o n each side. So w e can b alan ce С and H elem ents. T h e re are 3 С
atom s on the left, w e place 3 in front o f C O 2 .
A T T E N T IO N !
C 3H 8 + 0 2 -> 3 C 0 2 + H 20
N e v e r c h a n g e th e s u b ­
sc rip ts in . any fo rm u la to W e place 4 in front o f H 20 to balance H atom s.
b a la n c e the n u m b e r o f a t­
C 3H 8 + 0 2 -> 3 C 0 2 + 4 H 20
o m s on b o th sid e s o f the
e q u a tio n . B e c a u s e c h a n g ­ T h e e q u a tio n is still n o t b alanced. T h e to tal n u m b e r o f О ato m s on the
in g th e su b s c rip t c h a n g e s rig h t is 10, 6 in 3 C 0 2 and 4 in 4 H 20 ,
th e id e n tity o f th e c o m ­
T o balan ce 0 ,w e place 5 in front o f 0 2.
p ou n d . R ecall th at H 2 O and
C3H 8 + 5 0 2 -> 3 C 0 2 + 4H 20
H2O 2 a rc d iff e re n t c o m ­
p o u n d s. C heck:
i-------------- c o efficie n t 3 <— С atom s —> 3
3C 02
8 <— H atom s —> 8
1—'■ su b s c rip ts
10 « - О atom s -> 10
S ince th e n u m b er o f each kind o f atom s on both sides o f the equation are
th e sam e, th en the equation is a balanced equation.
M u ltip ly in g the co efficien ts o f a balan ced eq u a tio n by a co m m o n facto r
does n o t d istu rb its balance.
2C 3H g + Ю СО2 - » 6 C 0 2 + 8H 20
100C3H 8 + 5 0 0 C 0 2 - а ЗООСО2 + 400H 20
T h e equations given above are also balanced equations. In practice, h o w ­
ev er, w e n o rm ally use the sm allest p o ssible set o f w hole n u m b e r co efficien ts
to balance an equation. ^
C3H 8 + 5 0 2 —> 3 C 0 2 + 4H 20

E X A M P L E 4.3 Writing and Balancing Equation

Problem : In laboratory, oxygen gas may be generated by decomposing potassium chlorate into potassium
chloride and oxygen gas. Write a balanced equation describing the reaction.
Solution ; From the information in the problem we may write a word equation.
Potassium chlorate —> Potassium chloride + Oxygen gas
Substituting the names o f substances with their formulas we get:
КСЮ 3 -» KC1 + 0 2 (skeleton equation)
The most complex substance in the equation is KC103, so we assume its coefficient to be 1, and adjust the coef-
 Chemical Reactions 109

ficientsof KC1 and O 2 according to the coefficient of KCIO3. The inspection of the reaction shows that К and Cl
atoms have already balanced. There are 3 "O" atoms on the left but 2 on the right. This imbalance o f О atoms
can be eliminated by writing 3/2 in front o f O 2, on the left-hand side as follows.
КСЮ 3 -> KC1 + 3 /2 0 2
Check : 3 <— К —> 3
1 <- Cl -> 1
3 <- О -» 3/2x2=3
This equation is now completely balanced. Such equations with fractional coefficients are common in chemistry.
But it is more convenient to change these coefficients to whole numbers by multiplying the coefficients on both
sides by the denominator of the fractional coefficient. In this case, it is 2.
2KC10 3 -> 2KC1 + 3 0 2
Another approach to balance the equation may be as follows. Oxygen appears once on both sides of equation, its
number is 3 on the left and 2 on the right. The least common multiple of 3 and 2 is 6 . Then, the number o f О

2KC10 3 -> KC1 + 3 0 2

Later, 2 is placed in front of KC1 to balance К and Cl atoms.
2KC10 3 -4 2KC1 + 3 0 2

E X A M P L E 4 . 4 B a la n c in g E q u a tio n s In v o lv in g P o ly a to m ic Io n s
Problem : W ater that contains dissolved calcium compounds is called "hard” water, meaning that it is hard to
use soap in such water. The soap forms a scum with the calcium compound. One way to "soften" such water is
to add sodium carbonate, ИагСОз. It removes the calcium by forming calcium carbonate, which is insoluble in
water. Balance the equation that illustrates this reaction.
Ca (N 0 3)2 (aq) + N a ^ O j (aq) C aC 0 3 (s) + N aN 0 3 (aq) ( unbalanced)
calcium sodium calcium sodium
nitrate carbonate carbonate nitrate
Solution : C a ( N 0 3)2 (aq) + N a 2C 0 3 (aq) -> C a C 0 3 (s) + N a N 0 3 (aq)
C a(N 0 3)2 (aq) + N a 2C 0 3 (aq) -> C a C 0 3 (s) + 2 N a N 0 3 (aq)
C a (N 0 3)2 (aq) + N a 2C 0 3 (aq) -> C aC 0 3 (s) + 2 N a N 0 3 (aq)
C a (N 0 3)2 (aq) + Na 2C 0 3 (aq) C a C 0 3 (s) + 2N aN 0 3 (aq)
C a (N 0 3)2 (aq) + Na 2C 0 3 (aq) -> C a C 0 3 (s) + 2 N a N 0 3 (aq)
Since О appears in all compounds its balance is left to the last.

EXERCISE 4.2 Balance each o f the following equations.

b) C 2H 6 j ? 0 2 -> £C 0 2 -&H20
d # P 2H 4 -*4PH 3 + p 4
0 S2C12 + NH 3 -> n 4s 4 + NH 4C1 + s 8
h) Ag + 1IHNO3 -* A g N 0 3 +£NO + H20
110 Chapter 4
..... ..... . ............ .. ...... .та.,;,„::,,у^,..„т..М
а;;,л
E X A M P L E 4.5 D eterm ining Form ula o f a Substance from B alanced Equation
Problem : W hat is the molecular formula of the compound represented by X in the following balanced equa­
tion ? 4X + 5 0 2 —> 4NO + 6 H2O
Solution : The number of atoms of each kind must be the same on either sides o f the equation. Let us find
the number o f atoms in X.
4X + 5 0 2 -> 4NO + 6 H 2O
? <— N —> 4
12
10 О -> 4+6=10
To have equal number o f N and H atoms on both sides, 4 X should contain 4 N and 12 H atoms. Then 1 X
should have 1 N and 3 H atoms or its formula must be N H 3.

EXERCISE 4.3 Determine the formula of X in the following balanced equations,

a) 9Fc 20 3 + 2NH 3 -» 6 X + N 2 + 3H20 b) 2 M n0 2 + 4X + 0 2 -» 2K 2M n 0 4 + 2H20
с) 2K M n0 4 + 16HCI -> 2M nCl 2 + 2KC1 + 5X + 8H20 d) Cr 20 3 + 3X -> 2CrCl 3 + 3CC120
c) As 2S 3 + 12N aN 0 3 + 3Na 2C 0 3 -» X + 3Na 2S 0 4 + 3 C 0 2 + 12NaN0 2
a )F e jO 4 b )K O H c)C l 2 d) CCI 4 e)A s j О j

4.3 TYPES OF CHEMICAL REACTIONS

In discussing chem ical reactions it is useful to establish categories o f re­
actions.
1. C om b u stion reactions: In c o m b u stio n rea ction s, carbon-
hydrogen com pounds (hydrocarbons) or carbon -h yd rogen -oxygen co m ­
pounds bum com pletely in oxygen gas to produce carbon dioxide and water.
C2H 6 (g) + 7 /2 0 2 (g) -> 2 C 0 2 (g) +3H 20 (g)
C2H5OH (1) + 3 0 2 (g) -> 2 C 0 2 (g) + 3H 20 (g)
2. C om bination (or synthesis) reactions : In com b in ation reac­
tions tw o or m ore substances (either elem ents or com pounds) react to form a
T h ree im p o rta n t types o f
more com plex substance.
r e a c tio n s - w e have not
m en tio n ed h e re are: H 2 (g) + Cl 2 (g) - > 2HC1 (g)

-p re c ip ita tio n re a c tio n s 3. D ecom position reactions : In d ecom p osition reactions a sub­
stance is broken down into two or more sim pler substances.
-a cid -b ase re ac tio n s
2 КСЮ 3 (s) - > 2 K Q (s) + 3 0 2 (g)
-o x id a tio n -re d u c tio n re­
a c tio n s . 4. Displacement reactions : In displacem ent reaction one elem ent
in a compound is replaced by an atom o f another e le m e n t.
M g (s) + 2HC1 (aq) M gCl 2 (aq) + H2 (g)
5. Metathesis reactions : In m etathesis or double displacem ent re­
actions, an exchange occurs betw een tw o reactants.
A g N 0 3 (aq) + NaCl (aq) > A gC l (s) + N a N 0 3 (aq)
 Chemical Reactions 111

4.4 CALCULATIONS BASED ON EQUATIONS

A balanced chem ical equation conveys a lot o f information that can be ap­
plied to chem ical calculations concerning the quantities o f substances involved
in chem ical reactions. Let us see what information w e can derive from a bal­
anced equation.
2A1 (s) + 6HC1 (g) -> 2A1C13 (s) + 3H 2 (g)

2A 1 (s) + 6HC1 (g) ^ 2A1C13 (s) + 3H 2 (g)

! In terms of
\ :
\
( 1) molecules : 2 molecules 6 molecules 2 molecules 3 m olecules
\;
6 mol 2 mol 3 mol
; ( 2) moles
: 2 mol
(3) mass : 2x27 g 6x36.5 g 2x133.5 g 3x2 g
: (4) volume at STP . -------- 6x22.4 L ............. 3x22.4 L
(for gases only.) 6 volumes 3 volum es

W e see that the coefficients in a balanced chemical equation indicate the

num ber o f molecules or number o f moles o f m olecules (or atom s fo r elem ents)
o f substances, that react or are form ed.
It is quite easy and straightforward to do calculations about chem ical re­
actions by m eans o f the information provided by a chem ical equation. The fo l­
lo w in g exam ples illustrate how to u se chem ical equations in so lv in g prob­
lem s.

4.4.1 C A L C U L A T IO N S A B O U T Q U A N T IT IE S
OF R EACTANTS AND PR O D U C TS
W e m ay calculate the quantity o f any reactant or product in terms o f
m ole, m ass, particle number, and volum e. In solvin g problem s w e shall u se
the follow in g procedure.
STEP I : W rite the balanced equation.
S T E P II : C onvert the quantity o f given substance into moles.
S T E P I I I : F ind the mole num ber o f desired substance by using the re­
lationship betw een coefficients o f given substance and desired substance in
the balanced equation.
S T E P IV -.Convert the m oles o f desired substance into the desired units.

S T E P II STEP III
“I С
x AW (or MW) = m

given A n<jCs i red -> X Na = N

-> X 22.4 = V (at STP) ,
VIA COEFFICIENTS DESIRED
112 Chapter 4

E X A M P L E 4.6 W o r k in g W ith M o le R e la tio n s h ip s

Problem : When mercuric oxide, HgO, is heated it releases mercury and oxygen gas. How many moles of ox­
ygen gas will be produced from the decomposition of 4 mol of mercuric oxide ?
Solution: We will follow the steps described in section 4.4.1 to solve the problem.
Step I : The balanced equation is 2HgO -» 2Hg + O 2
Step I I : The substance is given in mole units.(No need for unit conversion)
Step I I I : The number of moles of O 2 produced by 4 mol of HgO is :
From the coefficients of the substances in the balanced equation wee see that 1 mol of O 2 is produced when 2
mol of HgO decomposed.
If 2 mol of HgO produce I mol of O2 1 . TT ^ 1 mol 0 2 „ , , л
) x.. =_ 4 nidi HgO
^ -x — -= 02 mol
1 of О ,
then, 4 mol of HgO will produce x J 2 moHTgO
rnoHTgO
Step IV : Since the unit of O 2 is asked in molps, there is no need for unit conversion. Recall that we can use the
dimensional analysis method in calculations. In this method we use the following pattern :
Щ |1 Ш 1 :: ' 2 О :‘. V - - - - - V 'W .. . . / V V i:,;. . ; !' : ' V/ / ' ; i . '- . ; 'T '. : : 2 —- " ■■ ■" - V y : /,, , |p

The quantity of the desired substance

The quantity of the given x in desired units in the balanced equation _ qie quantity of desired
substance and its units The quantity of the given substance in the substance in desired units
balanced equation expressed in the given units

In our problem ; given : 4 mol of HgO desired : ? mol o f O 2

the coefficients come from balanced equation
1 m of 0 2 «
4 m oTH gQ x / -------= 2 mol 0 2
2inoTH g0
E X A M P L E 4.7 W o r k in g w ith M o le R e la tio n s h ip s
Problem ; How many molecules o f potassium chlorate are required in the preparation of 6 mol of oxygen
gas ? 2KC10 3 2KC1 + 3 0 2
Solution: The solution chart is : 6 mol 0 2 —>?mol КСЮ 3 -» ? КСЮ 3molecules
2 mol of КСЮ , are required for 3 mol o f O , q
1 Г v r - m С rC 1 f I x = , = 4 mol of КСЮ 3 are required
x mol of KCIO 3 6 mol of 0 2 J 3

The number of m olecules of KC10 3 is :

1 mol contains 6.02x 1023 molecules. Then, 4 mol KC10 3 = 4x6.02xl0 23 = 2.408xl024 KC10 3 molecules

2W W W . T o W W hen aluminum is heated with sulfur, aluminum sulfide is formed.

a) Write the balanced equation .
b) Calculate the number of moles of A1 that combines with 6 mol of S
c ) Calculate the number of aluminum sulfide molecules produced from 0.4 mol of Al.
а ) 2 Л I + 3 S ' —* Л 12 S 3 b ) 4 m o l c ) l .2x10^ *m o l e с u l eл

EXAMPLE 4 . 6 W ork in g with M ass R elation sh ip s

Problem: If 212 grams of sodium carbonate react with calcium hydroxide,how many grams o f sodium hy­
droxide are formed ? Na 2C 0 3 +Ca(OH )2 > 2 N aO H +C aC 0 3 N a 2 C 0 3 = 106g/mol, NaOH = 40 g/mol
 Chemical Reactions 113

Solution ; The solution chart is : 212 g Na 2C 0 3 -> ? mol Na 2C 0 3 -> ? mol NaOH ■-» ? g N aOH
I- n Naro = -------- ~— —2 mol
f 3 106 g/mol

II. The equation indicates that 1 mol N a 2C 0 3 produces 2 mol o f NaOH

j- x = 4 mol of NaOH
then, 2 mol Na 2C Q 3 produce_______ x

III. W eight o f NaOH = n x MW = 4 mol x 40 g/mol = 160 g NaOH are produced

We can solve the problem without using mole relationship. W e interpret the quantity of the given substance in
the given units and the quantity of the desired substance in the desired units in the balanced equation. Here the
mass o f Na 2C 0 3 is given therefore we interpret it as the mass of 1 mol o f N a 2C 0 3, 106 g. The mass of NaOH
is asked therefore, the amount of NaOH in the balanced equation, which is 2 mol, is expressed in grams,
2x40=80 g.
NajCOj -------- > 2 NaOH
If 106 g gives 80g 1
212 g will give x g \ x ~ = g NaOH

EXERCISE 4.5 How many grams of sodium- hydroxide will react with 49g of phosphoric acid ?
H ,P 0 4 =98g/mol , NaOH=40g/mol . The equation is : H ,P 0 4 + 3 N aO H > 3H 20 + N a ,P 0 4 60 g N a O H

EXA M PLE 4 . 9 W e ig h t - V o lu m e R e la tio n sh ip s

Problem : How many liters o f oxygen (at STP)are liberated by heating 490 g of potassium chlorate ?
К С Ю 3 = 122.5g/mol 2KC10 3 -> 2KC1 + 3 0 2
Solution ; 490 g KC10 3 Л ? mol KC10 3 4 ? mol 0 2 Щ ? L 02
I. nj^^jQ^ = 490/122.5 = 4 mol II. 2KC10 3—» 2KC1+ 3 0 2 (g)
2 mol of КСЮ , liberate 3 mol of О , 1 , , . _
J zf x = 6 mol of 0 2
4 mol o f KC10 3 x J
III. At STP,1 mol of gas occupies 22.4 L, then, 6 mol of gas will occupy (6x22.4) or 134.4 L of oxygen are
liberated
OR 2KC10 3 -> 3 0 2 + 2KC1
2x122.5 g 3x22.4 L
134.4 L 0 2 are liberated
490 g x L

EXER C ISE 4 . 6 Consider the reaction M n 0 2 + 4HC1 -> MnCl 2 + Cl 2 + 2H20

How many grams of M n 0 2 are required to produce 5.6 L of Ci2 at STP I M n 0 2 = 87 21. 75 g

EX A M PLE 4 . 1 0 W o r k in g w ith M ole R e la tio n s h ip s

Problem : If 152 mL of liquid carbon disulfide (density = 1.25 g/mL) are burned completely, a) How many
liters of S 0 2 at STP are formed ? b) How many liters o f 0 2 are required at STP ? CS 2 = 76 g/mol
CS 2 + 3 0 2 C 0 2 (g) + 2 S 0 2 (g)
114 Chapter 4

Solution : a) (152 mL, d = 1.25 g/mL) -> ? g CS 2 -> ? mol CS 2 - > mol S 0 2 -» ? L S 0 2
I. m = d x V = 1.25 g/mL x 152 m L = 190 g II. r s = .... 190 8 ..= 2.5 mol C S ,
n’CS
76 g/mol

III. 1 mol CS 2 forms 2 mol S 0 2 s IV. 1 mol S 0 2 at STP 22.4 L 'i

2.5 mol CS 2 x j x = 5 mol S 0 2 5 mol S 0 2__________ x J x = 112 L

b) 2.5 mol CS 2 > ? mol 0 2 -> ? L 0 2 at STP

1 mol CS 2 requires 3 mol 0 2 л 1 mol 0 2 at STP 22.4 L v
2.5 mol C S 2__________ x J = 7-5 mol 0 2 ^ 7^5 mol 0 2 x \ x ~ ^ ^

E X A M P L E 4.11 V o l u m e - V o l u m e R e l a t i o n s h i p s
Problem : How many liters of carbon dioxide are formed from the combustion of 60 liters of ethylene gas,
C 2 H4 ? Recall that the combustion of any compound made from С and II elements produces carbon dioxide and
water vapor.
Solution : When we are given a volume problem, we recall Avogadro's Law. Since" Equal volumes of gases
under the same conditions of temperature and pressure contain the same number of molecules", we would expect
the relationship in the volumes o f the gases to be the same as the relationship in the number o f molecules.
(These particular calculations apply only to gases ).
C 2H 4 (g) + 3 0 2 (g) 2 C 0 2 (g) + 2 H20 (g)
1 molecule 2 molecules
1 volume 2 volumes
1 liter 2 liters
60 liters ~ }1 120 liters of CO , are formed.

EXER C ISE 4.7 G, vcn the balanced equation : N2 (g) + 3H 2 (g) —> 2NH 3 (g)
Calculate a) the volume of H? that reacts with 12 L o f N 2
b) the volume of NI-I3 produced from 4 L of N2
c) the volumes o f N 2 and H2 to produce 60 L of NH 3
A «-.nnc that all volume measurements arc made under identical conditions.
a)36L b)HL c ) 3 0 L N 2 , 9 0 1. H у

E X A M P L E 4 .12 U n d e r s t a n d i n g P r o b l e m S o l v i n g C o n c e p t
Problem : Aluminum reacts with hydrochloric acid and produces aluminum chloride and hydrogen gas.
Answer the following questions for 2.7 g of aluminum used in the reaction. Al=27, Cl=35.5, H=1
a) How many grams of AICI3 will be produced ? b) How many moles of HCI are used ?
c) How many molecules of H 2 are formed ? d) What is the volume of H 2 measured at 27°C and 950 torr ?
Solution : The balanced equation is 2Al + 6HC1 2AlCl3 + 3H 2
a) 2.7 g Al —> ? mol Al —> ? mol AlCl 3 —> ? g AICI3
 Chemical Reactions 115

I. n - 2.7 g _ q д mQj II. 2 mol Al produce 2 mol AICI3 v

27 g/mol
b
' a , i A i
0.1 mol Al x
1
mol AICI3 J
a m i i x ~ ° -l mol AICI3

III. 1 mol AICI3 is 133.5 g then 0.1 mol A1C13 is 0.1x133.5 = 13.35 g A1C13

b) 0.1 mol Al —> ? mol HCI => 2 mol Al 6 mol HCI j x = 0.3 mol HCI are requried.
0.1 mol Al_________ x

c) 0.1 mol Al —> ? mol H 2 —» ? H2 molecules

2 mol Al 3 mol H 2
x = 0.15 mol H2
0.1 mol Al x
1 mol H2 contains 6 .0 2 x l ()23 molecules then 0.15 mol H 2 contains (0.15 x 6.02xl023) or 9.0 3 x l0 22 molecules
d) In part (c) we have found that 0.15 mol of H2 was produced from 2.7 g of Al. The volume of 0.15 mol o f H 2
at 27°C and 950 torr i s : D„ . „ _АЛ
V= = 0-15 mol x 0.082 L.atm /m ol.K x 300 К _ 2 95 p
P (950/760) atm

EXERCISE 4 . 8 The combustion o f ammonia, NH 3 (g), produces NO (g) and H20 (g)
a) Write the balanced equation representing the reaction.
/
b) How many moles of H20 arc produced when 2 mol of NH 3 is burned ?
c) How many moles of 0 2 are requried to react completely with 3 mol of NH 3 ?
d) How many grams of NO are produced when 16 grams of 0 2 are used.
c) How many grams of H20 arc formed when 8.96 L of NH 3 at STP is completely burned ?
f) How many liters of NO tit STP will be produced when 1,8 x l ()23 NH 3 molecules arc burned ?
g) How many liters of 0 2 and how many liters of air are required to burn 20 L. of NH 3.
(Assume the identical conditions. Recall (hat 1/5 of air is 0 2 by volume)
a ) 4 N / / }+5 О A' О + 6 H j O b)3mo! c)3.75mol il)!2g e)10.8g f)6.72L g)25 L, 1251.

4 .4 .2 R EA C TIO N S IN V O L V IN G LIM ITIN G R E A G EN T S

In so m e cases all o f the re acta n ts in a re ac tio n m ay n o t b e co n su m ed

co m p letely b ecau se the am ounts o f them are n o t p laced in c o rre c t ratios. In
such a case, the reaction continues until one o f the reactants is com pletely used
up. The reactant that is consum ed fir s t is called the lim it in g r e a c t a n t or li ­
m i tin g r e a g e n t and the reactant that is partially consum ed or partially unre­
acted is called the e x c e ss r e a c t a n t . T h e a m o u n t o f p ro d u c t th a t can be
form ed b y th e reactio n is determ in ed by th e lim itin g reactan t. T h erefo re, in
so lv in g th e p ro b lem s in v o lv in g ex cess re ag en t, first th e lim itin g rea g e n t is
iden tified and the calculation o f the am ount o f product produced by the reac­
tion is based on the quantity o f the limiting reactant.
T h e p rin cip le o f the lim iting reagent is an alogous to the relatio n sh ip b e ­
tw een the n u m b e r o f stam ps available and the n u m b e r o f letters to be m ailed.
If th ere are 7 letters and only 5 stam ps, then the m ax im u m n u m b e r o f letters
116 Chapter 4

that can be m ailed is five. T he n u m b er o f stam ps determ ines the n u m b er o f le t­

ters th a t can be m ailed. T h e stam ps are analogous to th e lim itin g reag en t and
the letters available are analogous to the excess re ac tan t b ec au se 2 le tte rs re ­
m ain unm ailed because o fla c k o f stam ps.
T h e principle described is illustrated in the follow ing exam ples.

E X A M P L E 4 .13 W o r k in g w ith L im itin g R e a g e n t

Problem : The mixture of 2 mol of H 2 and 2 mol of 0 2 gases are ignited to obtain water. Which reactant is
limiting ? Which is the excess reactant ? How much water will be produced ?
Solution : First, assume that all of the H 2 will react and calculate the amount o f 0 2 required for 2 mol of
H2,
2H 2 (g) + 0 2 (g) -» 2H20 (1)
According to the balanced equation we see that 1 mol of 0 2 is required for each 2 mol of H2. Then 1 mol 0 2 can
be consumed by 2 mol of H2, and 2-1=1 mol of 0 2 remains uncreacled. Since all the H 2 is used up, H 2 is the li­
miting reactant, and 0 2 is the excess reactant (1 mol 0 2 is left alter the reaction has completed.)
The amount of water produced is determined by H2, the limiting reactant, using the following the usual steps.
2 mol H 2 -> ? mol H20 -> ? g H20
The number of grams of H20 produced by 2 moles of H 2 is
2 mol H2 2 mol H20 q i« a
2 z \ x = 2 mol H 20 =s> 2 mol H 20 x = 3 6 g H 20
2 mol__________ x J 1 mol H 20
Another approach to determine the cxces or limiting reactant is to divide 'he actual mole numbers (the mole
number given in the problem) by the coefficient shown in the balanced equation.
2 mol H 2 2 mol 0 2 .
I - l --2
2 1
the reagent which gives a smaller proportion (here H2) is the limiting reagent and the other is the excess reagent.

E X A M P L E 4.14 W o r k in g w ith L im itin g R e a c ta n t

Problem : Carborundum, SiC, is used as an abrasive. It is formed by the combination of S i0 2 and carbon,
according to the reaction : S i0 2 + 3C —» SiC + 2CO W hat mass of SiC is formed from 6 grams of S i0 2 and 6
grams of С ? Si=28, C=12, 0 = 1 6
Solution : In this problem, the amount of S i0 2 and С are given but the product SiC is asked. W e must find
first which reactant is in excess and which one is limiting.
The mole numbers of the reactants are ;

6 g S i 0 2—> n Si0 = -5 L _ = •— — = 0.1 mol and 6 g C = > n c =-— — — = 0.5 mol С

bl° 2 MW 60 g/mol . 12 g/mol

Assume that all S i0 2 is used up. The mole number of С required for this process is :
S i0 2 + 3C -> SiC + 2CO
1 mol 3 mol
0.1 mol x } : 0.3 mol С needed
 Chemical ReaQtions 117

Since we have 0.5 mol С available then 0.5-0.3=0.2 mol С will remain excess. The limiting reactant is the
S i0 2. The amount o f SiC produced is found by using ihe limiting reactant as follows.
S i0 2 + 3C -» SiC + 2CO
1 mol 1 mol
| x = 0.1 mol SiC is produced
0.1 mol_______ x_
O ,т
The mass of 0.1 mol SiC is : 0.1 mol SiC x — -4 g SiC is produced
1 mol SiC

E X E R C I S E 4 . 9 How many grams o f water are produced when 4 g of H2 and 8 g 0 2 are reacted ? 9 />

EXAMPLE 4 . 1 5 W o r k in g w ith V o lu m e R e la tio n s h ip s

Problem: Given: N 2 ( g ) +3 H2 (g) -> 2NH 3 (g)
If 20 L of N 2 and 15 L of H 2 gases at the same conditions are reacted, which gas will be excess and how many
liters ?
Solution: We have learned that the ratio of the number of moles is the same as the ratio o f volumes.
N2 + 3H 2 -> 2NH . n2 + 3H 2 -s. 2N H 3
1 mol 3 mol 1L 3L 1
1L 3L l x L 15 L j X= 5L
20 L x L, ) X= 60L

60 L o f H 2 are needed.W e have only 5 L of N 2 are needed. We have 20 L.Then it is

15 liters. H 2 is lim iting reactant in excess.(20-5) or 15 L o f N 2 rem ain unreacted.

EXAMPLE 4 . 1 6 W o r k in g w ith L im itin g R e a g e n t

Problem : Given : N 2 (g) + 3H 2 (g) -» 2NH 3 (g)
3.01xl0 23 molecules of nitrogen and 3.36 L of H 2 at STP are reacted.How many grams of NH 3 are produced ?
Solution : We will find the limiting reactant first.
23
3 .0 1 x 1 0 ,
n N = — — -------= 0.5 m ol, n H = 'M 6Jk = 0.15 j
2 23 2 2.24 L
6.02 x 10

N2 + 3H 2 > 2N H 3 N2 + 3H 2 -» 2N H 3
1 mol 3 mol 3 mol 2 mol
x = I. 5 mol o f H2 needed. \ x = 0.1 mol of N ll;
0.5mol x 0-15 mol x
isproduced.
Wc have only 0.15 mol, then it is ihe limiting reactant. т ^ ц =0.1 m olx17g/m ol=l.7g

E X E R C I S E 4. 1
2Al + 6 HBr -> 2A lBr 3 + 3H 2
If 4 mol o f Al and 9 mol of HBr are allowed to react (a) which of the two reactants is the limiting one ? (b) How
many motes of the excess reactant arc left at the end of reaction ? (c) What is the maximum mole number of H2
obtained ? a ) l l l i r b ) l m o l , t I c) 4. S m o l
118 Chapter 4 t
EXAMPLE 4 . 1 7 W o r k in g w ith L im itin g R eagent
Problem ; 18 g of С and 8 g of oxygen are reacted to form C 0 2. Which clement and how many grams re­
main behind ?
Solution: n c = 18/12 = 1.5 mol n o 0 =8/32 = 0.25 mol. Assume that all С is used in the reaction. The
mole number of O 2 required is :
С + 02 >C 02
1 mol 1 mol
, f x = 1.5 mol of 0 ,
1.5 mol x J z
But we have only 0.25 mol 0 2, then 0 2 is not enough. The 0 2 will be used up completely. This is the limiting
reactant. 0.25 mol 0 2 can burn 0.25 mol C. W e have 1.5 mol C, then 1.5-0.25=1.25 mol of С will remain be­
hind. This is the excess reactant and its mass is: m e = nxAW= 1.25 m olxl2g/m ol = 15 g.
Or you divide the mole number of each reactant by its coefficient in the balanced equation

for С => = 1.5 For 0 2=> = 0.25

1 1
0 2 has the smallest ratio then it is the limiting reagent. С is the excess reagent. The quantity of С remained at
the end of the reaction may be found by following the procedure.
0.25 mol 0 2 —> ? mol С fused) —> ? mol Г (excess') > g Г excess

EX ER C ISE 4.11
G iven the reaction 2 H 2S (g) + 3 0 2 (g) —» 2M20 (g) + 2 S 0 2 (g). T he quantities o f reactants o f the reaction arc
given below .For each o f the follow ing, determ ine the excess reactant and the m axim um gram s of w ater produced.
a) 2 mol o f H2S and 4 mol o f 0 2 г b) 4 mol o f H2S and 6 mol o f 0 2
c) 8.5 g o f H2S and 9.6 g o f 0 2 d) 6.02 x H2S m olecules and 6.72 L 0 2 at STP
c) 4.48 L H2S at S T P and 19.2 g 0 2 0 17.92 L H2S a t STP and 13.44 L 0 2 at STP
a ) (> 2 , 3f> X b) none, 72 x с )/ / >S, 2.6 f> (1)0 у, I -S g e ) O i , 2.6 x J)H 2 5, 7.2x

E X E R C I S E 4 . 1 2 G iven the reaction : As.tO (, + 4 Ь + 41-ЬО -» 2A s 20 2 + 8H1.

W hat is the m axim um gram s o f HI produced if 2 mol o f each of the reactant are reacted ? H I=128 512 x

EX ER C ISE 4 . 1 3 N itric oxide, N O , is prepared acco rd in g to the follow ing reaction in laboratories.
3 K N 0 2 + K N O 3 + Сг 20 з —> 4N O (g) + ЗКоСгОд . C alculate the m axim um liters o f NO at STP produced by
the reaction o f 10 0 g o f each o f the reactant ? K:39, N: 14, Cr:52 35.14L

EXAMPLE 4 . 1 8 W o r k in g w ith M a ss - M o le R e la tio n s h ip s

Problem : Equal weights o f sodium and chlorine gas arc reacted in a closed container-to give 0.1 mol o f so­
dium chloride.Which clement will remain behind and how many grams ?
Solution : First wc have to find the grams of sodium and chlorinq which are needed to produce 0.1 mol of
NaCl.
Na + 1/2C12 -» NaCl mNa = 0.1x23 = 2.3 g
1 mol 0.5 mol 1 mol m et = 0.05x71 = 3.55g
x j = 0.1 mol X2 = 0.05 mol 0.1 mol .
 Chemical Reactions 119

2.3 g Na and 3.55 g Cl 2 are used in this reaction. The initial weights of them are equal. We will accept them as
3.55g of Na, 3.55 g of Cl 2 initally. (it is equal to the largest one.) In that case, all of the Cl2 will be used but
(3.55 -2.3) or 1.25 g of Na remain unreacted.

E X A M P L E 4.19 W o r k in g w ith M o le R e la tio n s h ip s

Problem .'Equal moles of aluminum and oxygen are reacted to give 20.4 g o f aluminum oxide. Which one
remains unreacted and how many moles ? AI2O 3 = 102 g/mol
Solution : n Al20 3 = 20.4 g/102 g/mol = 0.2 mol
How many moles o f Al and 0 2 are used to produce 0.2 mol of Al2 0 3 ?
2 Al + 3 /2 0 2 -> A12 0 3
2 mol 1.5mol 1 mol
x 1 = 0 .4 mol X2 = 0.3 mol 0.2 mol
The number o f moles o f Al and 0 2 were equal initially. We accept that each o f them was 0.4 mol. In that case all
aluminum will be used, but (0.4 - 0.3) or 0.1 mol of 0 2 will remain unreacted.

EXERCISE 4.14 E qual volum es o f sulfur dioxide and oxygen gases arc reacted to give 5 liters o f sulfur
trioxide at the sam e conditions. W hich one rem ains unrcactcd and how m any liters ? 2.5 I. O2

4 .4 .3 R E A C T IO N S IN V O L V IN G IM P U R E
SU BSTAN C ES
In th e p receding sections w e have described how to calculate the quantity
o f a reactan t o r p ro d u ct in a chem ical reaction. T h ese calculations w ere based
o n the assu m p tions th at these reactants o r pro d u cts are 100 % pure. It is quite
d iffic u lt and n o t eco n o m ical to u se o r to p ro d u c e 100 % p u re su b stan ces in
ch em ical reactions. T h erefo re w e freq uently e n c o u n te r im p u re su b stan ces in
the reactio n s. In calculations in volving im p u re substan ces, w e first find th eir
100 % p u re eq u iv alen ts and then u se them in calculations. T h e fo llo w in g e x ­
am ples illustrate the principle.
E X A M P L E 4 .2 0 W o r k in g w ith Im p u r e R e a g e n t
Problem : W hat weight of HCI is produced when sulfuric acid reacts with 200 grams of 87.75% pure sodi­
um chloride according to the reaction : H 2SO 4 + 2NaCl —> Na 2S 04 + 2HC1 (assume that 12.25% o f the sample
is inert in the reaction) ? NaCl=58.5g/mol, HC1= 36.5 g/mol
Solution : (200 g, 87.75 % NaCl) -» ? g 100 % pure NaCl -> ? mol NaCl -> ? mol HCI -> ? g HCI

200 x “ p p = 175.5 g pure NaCl, n NaC1 = 175.5 g/58.5 g/mol) = 3 mol NaCl

H 2S 0 4 + 2NaCl >Na 2 S 0 4 + 2HC1

2 mol of NaCl 2 mol of HCI
3 mol of NaCl x = 3 mol o f HCI => m nci = 3 mol x36.5 g/mol = 109.5 g HCI
OR: 2N aC l > 2HC1
2x58.5g. 2x36.5g. x
/ x = 109.5 g of HCI will be produced.
120 Chapter 4

E X ER C ISE 4.15 How m any liters (at STP) o f oxygen can be liberated from 1700 gram s o f a solution
which is 3.0 % hydrogen peroxide by w eight ? T he equation is 2H 20 2 (I) 2H 20 (I) + 0 2 (g)
I l:0 ,= 3 4 g /m o l (Hint : (1700 g, 3% H 20 2) —> ? g 100 % pure H 2G 2 —> ? mol H 20 2 —> ? mol От —> ? L. at S I P)
16.8 I.

EX A M P LE 4.21 W o r k in g w ith Im p u re R eagent

Problem : H ow m any gram s o f H 2S 0 4 can be produced from 300 g o f FeS 2 w hich is 60 % pure by w eight ?
F e S 2 = 120 g/m ol H 2S 0 4 = 98g/m ol
Solution : (300 g, 60 % pure F eS 2 ) -> ? g 100 % p ure F eS 2 -> ? mol F eS 2 -> ? m ol H 2 S 0 4 -> ? g H 2S 0 4
3 0 0 x -^ -= 1 8 0 g n Fl.s - = 1 .5 mol
100 2 120
In this kind o f problem s, balancing the num ber o f the atom s o f the com m on elem en t is enough.In our exam ple
the com m on elem ent is S
F cS 2 2H ,S O ,
lm o l 2 m ol л
1.5 mo! x J x = 3 mol => m , , ^ = 3 m ol x 98 g/m ol = 294 g

E X A M P LE 4 .22 W o r k i n g w ith I m p u r e S u b s ta n c e
Problem: H ow m any gram s o f sodium chloride that is 90% pure are required to produce 73 g o f HCI acco rd ­
ing to the reaction below ? (N aC l = 58.5, HCI = 36.5)
N aC l + H 2S 0 4--> N a H S 0 4 + HCI
Solution : 73 g HCI -> ? m ol HCI -> ? mol N aC l ? g N aC l (100 % pure) -> ? g N aC l (90 % pure)
n HCt= = 2 m ol
36.5

N aC l + H 2S 0 4 > N a H S 0 4 + HCI
1 m ol 1mol г
, x = 2 m ol N aC l
x 2 m ol J

2 m ol N aC l x = 117 g NaCl (100 % pure)

1 m ol NaCl
The am ount o f im pure N aC l w hich is 90% pure is :
100 g o f im pure sam ple contain 90 g o f pure N aC l 1 , . . . . ... .
1 x = 117 x 100/90 = 130 g o f 90% N aCl is needed.
x_______________ ^___________ 1 1 7 g o f pure N aCl J

EXER C ISE 4.16 A 25 gram sam ple o f iron reacts with 200 g o f 14.6 % HCI solution by m ass. The re­
action is Fe + 2HC1 —> F-’e C h + H2. C alculate the percentage o f iron in the sam ple ? (A ssum e that im purities
are inert to HCI.) F e=56, H C l=36.5 89.6 ‘u

EXER C ISE 4.17 W hen art unknow n quantity o f m agnesium is reacted w ith HC'l, 4 .48 L o f H 2 al STP
together with som e m agnesium chloride are formed.
 Chemical Reactions 121

a) What mass of magnesium chloride is formed ?

b) If the sample of magnesium is 96 % pure, what mass of magnesium sample is used in the reaction ?
c) What mass o f HC1 solution that is 20 % HC1 by mass would it be required to produce 4.48 L of H 2 at STP?
Mg=24, Cl=35.5 a ) 1 9 g b) 5 g c ) 73 g

EXAMPLE 4.23 C a lc u la tio n s B a se d on th e S ta te o f E q u a tio n

Problem : Consider the reaction : Mg + 2HC1 —> M gCl2 + H 2
How many grams o f Mg sample that is 40 % pure are needed to fill a 44.8 L balloon with H 2 gas at 273°C and
3 atm pressure ?
Solution : W e will follow the following steps to solve the problem.
Data -» ? mol H 2 -» ? mol Mg -> ? g Mg (100 % pure) -» ? g Mg (40 % pure)

PV = nRT => n = — = — 3atm x 44.8 L _ 3 mol ^

RT 22 A L a tm x 546 K
273 mol К

Mg + 2HC1 -> M gCl 2 + H 2

1 mol 1 mol i
> x = 3 mol M g = > m M = 3 mol x 24g/mol = 72 g of pure Mg needed
x ___________________________3 mol J 8

Then, the amount o f impure magnesium is :

100 g sample 40 g Mg pure 1
r x = 180 g of 4 0 % pure Mg is needed.
x ____________72 g Mg pure J

EXERCISE 4.18 Hydrogen gas may be prepared according to the reaction :

4H 20 (g) + 3Fc (s) -> Fc30 4 (s) + 4H 2 (g) J
What volume of H 2 measured at 798 torr and 252°C can be prepared from the reaction of 20 g sample of iron,
that is 84 % pure, with steam. 1 6 . 4 /.

E X E R C ISE 4.19 When 20 g of iron is reacted with oxygen, 20 g o f iron (111) oxide is formed. W hat
percent of iron is reacted with oxygen ? Fe = 56, О = 16 70 %
(Hint: 20 g iron (111) oxide -> ? mol iron (III) oxide -» ? mol Fc -» ? g Fe -> ? % of Fe)

4 .4 .4 C O N S E C U T IV E R E A C T IO N S
In som e cases w e deal with the chem ical calculations that require a series
o f at least tw o or m ore chem ical equations. T he series o f these reactions is
called consecutive reactions. The follow ing tw o exam ples illustrate how to do
calculations about these reactions.
199. Chapter 4

E X A M P L E 4 . 2 4 W o r k in g W ith C o n s e c u tiv e R e a c tio n s.

Problem : The acetylene gas, C 2H 2, is an important raw material in the production of many important chem­
icals such as synthetic rubber, alcohol... It may be prepared from limestone, СаСОз, coke, C, and water accord­
ing to the following reactions.
I. C a C 0 3 CaO + C 0 2 The sign, Д, above the arrow indicates that heat
II. CaO + 3C -> CaC 2 + CO energy is used for the reaction to take place.
III. CaC 2 + H20 -» C 2H 2 + Ca(OH )2
Assuming an excess of all other reactants how many liters of C 2H 2 at STP can be obtained from 50 g СаСОз-
СаСОз = 100 g/mol.
Solution : The relationship between СаСОз (in reaction I) and .C2H 2 (in reaction (III)) is asked. The inspec­
tion of the reactions reveals that the CaO produced in reaction (I) is used in reaction (II). So the CaO produced in
the first reaction is the limiting substance in reaction II. The CaC 2 produced by reaction II is used in the produc­
tion of C 2H 2 in reaction III. Therefore, the CaC 2 produced by reaction II determines the quantity of C 2H 2 that
will be produced by the overall reaction. O r the solution chart of the problem will be as follows.

t by reaction II
50 g СаСОз ? mol СаСОз -» '■ mol CaQ ? mol CaC 2 -» ? mol C 2H2 ,-» ? L C 2H 2 at STP.
by reaction I by reaction III

50 g СаСОз => n = m/MW = 50 g/100 g/mol = 0.5 mol СаСОз

According to reaction I : According to reaction I I : According to reaction I I I :

С а С О з -> CaO + C 0 2 CaO + 3C -> CaC 2 + CO CaC 2 + H20 ~> C 2H 2 + Ca(OH )2
1 mol 1 mol 1 mol 1 mol 1 mol 1 mol
0.5 mol x 0.5 mol x 0.5 mol x
x = 0.5 mol CaO x = 0.5 mol CaC2" x = 0.5 mol C 2H 2
22.4
And the volume of 0.5 mol C 2H 2at STP is 0.5 mol x 11.2 L
1 mol

EXERCISE 4.20 КВЮ 4 may be prepared by the following series o f reactions.

I. Br2 + 2KOH -> KBr + KBrO + H20
II. ЗКВЮ —> 2KBr + KB 1O 3
III. 4K B r0 3 -> ЗКВЮ 4 + KBr
Assuming the excess KOH, how much Br2 in grams is needed to prepare 109.8 g КВЮ 4 by the above sequence
of reactions ? К = 39, Br = 80, О = 16 384 g

EXA M PLE 4 . 2 5 W o r k in g w ith C o n se c u tiv e R eactio n s

Problem ; Given the reactions
I. A14C 3 + 12H20 - > 4A1(0H )3 + 3CH 4
II. CH 4 + 2 0 2 > C 0 2 + 2H20
The methane gas that is obtained from 50 g impure sample of A14C 3 is required 38.4 g o f 0 2 to be completely
burned. W hat is the percentage purity of AI4C 3 in the impure sample ? AI4C 3 = 144

Solution : 38.4 g 0 2 4 ? mol 0 2 -> ? mol CH 4 -> ? mol AI4C 3 -> ? g A14C 3 > ? % AI4C 3

38.4 g 0 2=^ 38.4 g x = 1.2 mol O ,

32 g
 Chemical Reactions 123

C H 4 + 2 0 2 -> C 0 2 + 2H20 AI4C 3 + 12H20 -> 4A1(0H )3 + 3CH 4

1 mol 2 mol 1 1 mol 3 mol 1 n- 1 A1
j * . 0.6 mol CH 4 ^ j * = 0.2 m ol A I,C 3
x mol 1.2 mol

0.2 mol А14С з => 0.2 mol A l 4C 3x = 28.8 g A14 C 3

1 mol A14 C 3

The percentage purity is :

50 g impure sample 28.8 g AI4C 3
100 g impure sample x I x - 57.6 g AI4C 3 or 57.6 % pure

EXERCISE 4.21 Iron is prepared in the blast l'urnacc according to the sequence of these reactions.
2C + 0 2 -> 2CO
3CO + Fe 20 3 -> 2Fc + 3 C 0 2
Assuming the excess of 0 2, how many tons of iron can be obtained by the reaction of 5 tons of hematite ore,
Р’е 20 з , that is 80 c/i pure with I ton of coke ? Fc=56, 0= 16, C=12 2 .8 t ons

4 .4 .5 S IM U L T A N E O U S R E A C T IO N S
In som e cases w c deal w ith the reactions o f tw o o r m ore su b stan ces oc-
c u rin g at the sam e tim e. T h e se are called sim u ltan eo u s reactio n s. L e t us see
how to cope w ith the calculations about these sim ultaneous reactions.

E X A M P L E 4 .26 W o r k in g W ith S im u lta n e o u s R e a c tio n s

Problem : To burn 30 liters of a mixture of C 3H4 and C 3H 8 gases at STP, 140 liters o f 0 2 are needed at the
same conditions. Calculate the volume of C 3H 4 in the mixture.
Solution : Let x be the volume of C 3H4 in the mixture, then the volume of C 3Hg will be (30-x). Now let
us find the volume of 0 2 required for burning each gas in terms of x, and equate their sum to 140 L.
C 3H 4 + 4 0 2 -> 3 C 0 2 + 2H20 C 3H g + 5 0 2 -> 3 C 0 2 + 4H zO
1L 4 L 1 L 5 L
x L a (30 -x) L b
a = 4x L b = 5 (30-jc) L
Total volume o f oxygen = a + b = 4x +5( 30-x) = 140 => 4x + 150 - 5x = 140 => x = 10 liters of C 3H 4

EXERCISE 4 . 2 2 The complete combustion of a 13.44 L mixture of C 2H 4 and C 3H4 gases at STP pro­
duces 31.36 L C 0 2 under the same conditions. Find the mole number of each gas in the mixture. 0.4 and 0.2

E X A M P L E 4 .27 W o r k i n g w ith M o le - V o lu m e R e la tio n s h ip s

Problem : 11.9 g o f an alloy made from Al and Zn is reacted with sufficient amount of HCI and 8.96 L of
H 2 at STP arc produced. W hat is the amount o f Al in the alloy ?

Solution : Both Al and Zn react with HCI and liberate H2 gas

ПЦ = ^ 8:9I6 L -T = 0-4 mQl m 7n = * g mAl = (11.9 - X ) g

2 22.4 L/mol
124 Chapter 4

Zn + 2HC1 -> ZnC l 2 + h 2 A1 + 3HC1 А1СЦ + 3/2H 2

65 g 1 mol 27g 1.5 mol

* g a mol (11.9 - x ) g b mol

a=x/65 mol H 2 1.5 x (1 1 .9 - x )

b= mol H 2
27

1.5 x (If. 9 - *)■■- 0.4 V> X

a + b = 0 ..4 mol of H 2 => Ж + = 6.5 g Zn
65 27
mass of A!1 = 11.9 -x = 11.9 - 6.5 = 5.4 g

EXERCISE 4.23 A 20 gram alloy of Mg and A1 elements is reacted with HC1 and 24.64 L of ЬЬ at STP
arc produced. Find the percentage by mass of A1 in the mixture ? Both metal react with HC1 and produce metal
chlorides and hydrogen gas. Mg = 24, A1 = 27 96 %

EXERCISE 4.24 Both sodium, Na, and calcium, Ca, metals react with water to produce metal hydrox­
ides and H2 gas. If 4 moles of H2 arc obtained from 5 moles mixtures of sodium and calcium metals, calculate
the mole percentage o f sodium in the mixture. Na=23, Ca=40 40 %

4.4.6 D E T E R M IN IN G E M P IR IC A L FORMULA
In the previous ch apter w e have learned how to find the em pirical form u­
la o f a com pound w hose either m ass com position o r percentage com position is
k n o w n . B y m ean s o f the reactions o f a substance, esp ecially th e co m b u stio n
> reaction, w e m ay determ ine its em pirical form ula.

E X A M P L E 4.28 Finding Em pirical F o r m u la

Problem : W hen 2.2 g of a compound containing carbon and hydrogen is burned, 3.36 liters of C 0 2 at STP
arc produced. W hat is the empirical formula of the compound ?
Solution : To find the formula of a compound we have to know the mole number of each clement in the
compound. CxHy + ? O 2 - 6 ? CO 2 + ? H20
3.36 L CO 2 at STP -> ? mol CO 2 -> ? mol C - > ? g C - » ? g H - > ? mol H -> empirical formula
The number o f moles of CO 2 is : 3.36 L/22.4 L/mol = 0.15 mol CO 2
1 mol С
The number of moles of С in 0.15 mol of C 0 2is : 0.15 mol C 0 2x ----------------= 0.15 mol С
1 mol C 0 2

The mass of 0.15 mol of С is : 0.15 mol С x ^ ^ - = 1.8 g С

1 mol С
^compound = m e + m u , then the mass of H in the compound is: mu = mrornp - m e or т ц = 2 .2 - 1.8 = 0.4 g
The mole number of H in the compound is 0.4 g/1 g/mol = 0.4 mol H~|
Then, the empirical formula is :
C o . 15 H 0 4 = > C 15H 40 = * C 3H 8

E X E R C ISE 4.25 The complete combustion of 8 g of compound made from only С and H produced
26.4 g C 0 2. What is the empirical formula of the compound ? С = 12, 0 = 1 6 , H = ! C3H 4
 Chemical Reactions 125

E X A M P L E 4.29 F in d in g E m p ir ic a l F o r m u la
Problem : When 2.3 g of a compound containing С, H and О is burned completely, 4.4 g of C 0 2 and 2.7 g
of H20 arc produced. Find its empirical formula.
Solution : As described in example 4.28 the numbers of moles of С and H arc found by means of the masses
o l'C 0 2 and 1-ЬО. The mass of О in the compound is found by the difference. m 0 = mcomp - (m e + шц)
C xH y0 7, + ? 0 2 ? CO , + ? H20
2.3 g 4.4 g 2.7 g
1 mol C
'
n co = 4 .4 /4 4 =0.1 mol => 0.1 mol C 0 2x ----------- — : 0.1 mol С => m c = 0 .1 x 12 = 1.2 g
' 2 1 mol C 0 2

2 mol H
n и о = 2.7/18 = 0 .1 5 mol => 0.15 mol H 20 x 0.3 mol 11 •••:> m H= 0.3 x 1 = 0.3 g
I mol H20

m 0 = 2.3 - (1.2 + 0.3) = 0.8 g nQ = 0.8/16 = "0.05 mol О

Сo.i/o.os Н()3/005 O005/005 c 2n6o

EXER C ISE 4.26 When 1.76 g of a compound containing С, H and О is burned completely in oxygen
3.52 g of C 0 2 and 1.44 g of H20 are produced a) Calculate the empirical formula of the compound, b) If 0.05
mol of the compound is 4.4 g, what is the molecular formula of the compound ? С = 12, О = 16
с 2н 4о, с 4н 8о 2

E X E R C IS E 4.27 6 mol of 0 2 arc required to burn 1 mol of compound with a general formula of
C nH 2n+20 . What is the molecular formula of the compound ? C 4 I 180

4.4.7 ATOMIC WEIGHT DETERMINATION

B alanced chem ical equations m ay be used to calculate the atom ic w eights
o f elem ents.

E X A M P L E 4 .30 W o r k in g w ith B a la n c ed E q u a tio n a n d M o le C o n ce p t

Problem : Given: X (OH )3 + 3 HY — > XY 3 + 3H20
9.5 grams of X (OH )3 and 19.2 grams of HY combine completely and produce 2.7 grams o f H 20 . Find the
atomic weights of X and Y .
Solution : The molecular w eight of H20 is known. Then we start the solution of the problem with finding
the number o f mole of water.
2.7 g H20 -> ? mol H20 ? mol X(OH )3 —> MW of X(OH )3 AW of X
I— ?molHY -> MW o f HY —> AW of Y
п н 2о = 2.7 g/18 g/mol = 0.15 mol.
The equation indicates that
1 mol of X(OH )3 gives 3 mol of H20 If 0.05 mol of X(OH )3 weighs 9.5 g
x mol 0.15 mol of H20 1 mol of X(OH )3 x

x = 0.05 mol of X(OH )3 x = 190 g/mo1

X(OH )3 = 190 => X + 3 x 16 + 3 x 1 = 190 => X = 139 g/mol
126 Chapter 4

From the equation

3 mol o f HY give 3 mol of H20 If 0.15 mol of HY weighs 19.2 g
x mol 0.15 mol of H20 1 mol o f HY x
x = 128g/mol
x = 0.15 mol o f HY
HY = 128 => 1 + Y = 128 => Y = 127 g/mol

EXER C ISE 4.28 Given the reaction : XO 2 + Y(OH )2 —> YXO 3 + H20
3.2 g XO 2 reacts completely with 3.7 g Y(OH )2 to produce 6 g YXO 3. Calculate the atomic weights of the ele­
ments X and Y. 3 2 g / mo l , 4 0 g / m o l

E X E R C IS E 4.29 Given the reactions :

I. X + 2H 2S 0 4 -> XSO 4 + 2H20 + S 0 2
II. XSO 4 + 4KI -> 2X1 + I2 + 2K: S 0 4
When 19.2 g X is used in the above sequence of reactions,104.4 gof K 2SO 4 is produced. What is the atomic
weight of X? K2S 0 4 = 174 ( H i n t : 104.4 g K2S 0 4 -» ? mol K2S 0 4 -> ? mol X S 0 4 -» ? mol X -> AW of X)
6 4 g/m ol

EXERCISE 4.30 When 13.7 g of M 3O 4 was heated, it decomposed into 13.38 g MO and some O 2 gas.
W hat is the atom ic w eight of M ? 207 g/m ol
... .... .. ------

4.4.8 P R E S S U R E , V O L U M E C H A N G E S IN
REACTIONS
In c h em ical reactions th ere m ay be chan g es in the n u m b e r o f m o les o f
substan ces, and tem perature. C on seq u en tly som e chan g es take p la ce in p re s­
sure o f the gaseo u s substances.

E X A M P L E 4.31 C a lc u la tio n s B a se d on C o m b in e d G a s E q u a tio n

Problem : W hen 3 mol o f C 2H 6 and 1.75 mol of 0 2 gases are reacted in a closed container, C 0 2 and water
vapor are produced and the temperature rises from 27°C to 127°C during the reaction. W hat will be the final pres­
sure in the container if the initial pressure is 5 atm. ?
Solution : In this reaction the volum e remains constant. But the temperature and the total mole number
change. That is why the pressure will change. Before reaction:
P, = 5 atm, Tj = 27°C + 273 = 300 K, n , = 3 + 1.75 = 4.75 mol
During the reaction the number of moles o f gases changes. Now let us find the mole numbers of products and the
excess reactant.
2C 2H 6 + 702 -> 4C 02 + 6H20
2 mol 7 mol i
\ x, = 0.5 mol o f CH 4 used.3-0.5 = 2.5 mol of C 2Hfi remains unreacted
Xj 1.75 mol J
The mole numbers o f the C 0 2 and H20 produced are :
2C 2H 6 + 7 0 2 -> 4C 02 + 6H 20 2C 2H 6 + 7 0 2 -> 4C 02 + 6H20
7 mol 4 mol 7 mol 6 mol
1.75 mol x2 1.75mol x3
x 2 = lm ol o f C 0 2 formed x 3 = 1.5 mol of H20 formed
 Chemical Reactions 127

After reaction, n T = 2.5 mol C 2H 6 + 1 mol C 0 2 + 1.5 mol H20 = 5 mol

P2 = ? , T 2 = 127 + 273 = 400 K, n 2 = 5m ol
Writing the ideal gas equation for the conditions before and after the reaction and approportionaling them term by
term gives. „ _
Pi n ,x T i 5 atm 4.75 mol x 300 К p 7
— = —— — => --------- = - => P 2= / atm
P ? n 2x T 2 P2 5 mol x 400 К

EXER C ISE 4.31 A quantity of 68 g of NH 3 is mixed with 160 g o f 0 2 in a sealed container at 27°C.
When a spark is passed through the mixture al 227°C the reaction, 4NH 3 (g) + 3 0 2 (g) —» 2N 2 (g) + 6H20 (g),
takes place. By what factor does the pressure change inside the container during die reaction ? Assume that the
volume of the container does not change ? I'^ /l’i = 30/27

E X A M P L E 4 .3 2 Calculations Based on Partial Pressures

Problem: At a certain temperature, in a closed container there are 6.02 x 1023 nitrogen molecules, 2 mol of
0 2 gas and 4g of H2. The pressure of the mixture is measured as 5 atm. When an electric spark is passed through
the gas mixture, liquid water forms. If the container is cooled to the original temperature, what will be the total
pressure of the gases remained in the container ? P Il2o = 22 mmHg at the given temperature.

23

Solution: Before reaction : nN = ft — = 1 mol n 0 = 2 mol П]т = — — = 2 mol

6.02 x IQ2 2 2 S/mo1
and the total mole number of gases is nT = nNz + n0z + пц 2 = 1 + 2 + 2 = 5 mol
Let us find the changes in the mole numbers of H 2 and 0 2 during the formation of water.
2H 2 + 0 2 -> 2H20
2 mol 1 mol
| x = 1 mol 0 2
2 mol x mol
2 mol H 2 and 1 mol 0 2 combine to give water, and 2-1=1 mol 0 2 remains unreacted. At the end of reaction
the number of moles of gases in the container are : n ^ = l mol (It did not take part in the reaction)
n o 2 = 1 mol (1 mol is used. 1 mol remained excess)
П|3 ) = 0 (All hydrogen is used in the reaction)
пт = 2 mol

The number of moles of gases before and after reaction in the container is 5 and 2 respectively. Applying the
ideal gas equation to the situations before and after reaction gives :
P. n. n, о
_ b = _!>=> p , = _ ? x P.. => P t = - x 5 = 2 atm
P tl 2 n t 2 4 n Lt 1 1 2 5
During the reaction liquid water is formed, then, the total pressure in the container will be the sum of the pres­
sure of the gases and vapor pressure of water.
PT = р ,.|ч +■ P |j,f) = 2 atm + 22 mmHg = 1520 mmHg + 22 mm Hg =* PT = 1542 mmHg

EXERCISE 4.32 Gaseous phosphorus pcntachloridc decomposes into phosphorus trichloride and chlorine
gas at elevated temperatures. PCI5 (g) —> PCI 3 (g) + Cl 2 (g). What pressure will be developed in the container il
0.06 mol of PCI5 is decom posed by 75 % at 727°C in a 5 L container ? 1.72 ami
128 Chapter 4

4.4.9 C A L C U L A T IO N S A B O U T G A S E S
COLLECTED OVER W ATER
W e m ay also use the balanced equations to find the volum es o f gases col­
lected o v er w ater.

E X A M P L E 4 .3 3 W o r k in g w ith V a p o r P r e ssu r e an d S ta te o f E q u a tio n

Problem : A 1 gram impure sample of Mg is reacted with excess HC1 and the H2 produced by the reaction is
collected over water. If 820 mLof H 2 were collected at 27°C and 787 mmHg pressure, calculate the percentage of
Mg in the sample. PHz0 = 27 mmHg at 27°C
Solution : When a gas is collected over water, the given pressure is the total pressure of the gas and water
vapor. 787 mmHg -> P „ 2 -> n „ 2 -> nMg -> rnMg -> % Mg

PT = P H2 + PH 20 =* 7^7 = p n 2 + 27 => p n 2 = 760 mmHg = 1 atm

The number o f moles of H 2 which is collected over water may be calculated by using the equation
PV= n R T
1 atm x 0.82 L 1 .
n= = — mol
0.082 L Atm/mol К x 300 К 30

The grams o f Mg needed to produce 1/30 mol of H 2 arc :

Mg + 2HC1 -> Mg Cl2 + H2
1 mol 1 mol
^ x = 1/30 mol Mg
_x______________________________ 1/30 mol
If 1 g sample has 0.8 g Mg ( pure)
т м ё = n x AW = 1/30 mol x 24 g/mol = 0.8 g Mg (pure) => 100 g x
x - 80 g or % Mg = 80

EXERCISE 4.33 97.5 grams of zinc reacted with dilute sulfuric acid, H 2S0 4 , according to the reaction:
Zn + H 2SC>4 —> Z n S 0 4 + H 2 The hydrogen gas produced was collected over water. What is the volume of hy­
drogen gas measured at 740 mmHg and 23°C produced by the reaction ? P II?0 = 21 mmHg at 23°C. Zn = 65.
38.5 L
 Chemical Reactions 129

SOME NEW TERM S

Balanced equation is a chem ical equation hav­ E ndotherm ic reaction is a reaction in which
ing the same number o f atoms and the same net charge heat is absorbed from the surroundings as it occurs.
on both sides of an equation. E xotherm ic reaction is that w hich gives off
Chem ical change is a transform ation o f one or heat to the surroundings.
more subslance(s) into one or more new substance (s). Lim iting reagent is the reactant that is com-
Chemical equation is a symbolic representation sumed completely.
of a chemical reaction in which symbols and formulas Physical change is one in which the physical
are substituted for the name of reactants and products. appearance of a substance changes.
C hem ical reaction is a process in which one Products are substances whose formulas appear
set of substances (reactants) is transformed into anoth­ on the right side of a chemic,al equation.
er set of substances (products). Reactants are substances whose formulas appear
on the left side of a chemical equation.

R E V IE W Q U E S T IO N S

4.1 Classify each ihe following changes as . c) Fe +HC1 -> FeCl 2 + H 2

a) a physical change, or a chemical change d) Ag20 -> Ag + 0 2
b) an exothermic change or endothermic one
(a) I 2 (s) + energy I2 (g) 4.4 Which are always conserved in a reaction ?
(b) H20 (g) -> H 20 (1) + energy a) mass b) volume c) mole number
(c) N 2 (g) + 3H 2 (g) -> 2NH 3 (g) + energy d) the number of atoms e) the number molecules
(d) KC10 3 (s) + energy KC1 (s) + 3 /2 0 2 (g)
(e) C i 2H 220 n (s) + energy -> С ] 2Н 220 ц (aq) 4.5 Balance the following equations :
a JN a + SF 6 -> Na2S -KNaF
4.2 W rite a balanced equation for each of the fol­ b) NH 3 + 0 2 N 0 2 + H20
lowing changes c) С ю Н 8 4 0 2 -* ftC 0 2 +^120
a) W hen magnesium bum s in oxygen gas it pro­ d) P 40 6 -&I2 - * P 2I4 +!P 4O io
duces magnesium oxide e) CaSi 2 + SbCl3 —> Si + Sb + CaCl 2
b) Aluminum reacts with chlorine gas to give alu­ 1) PbS + P b S 0 4 -> Pb + s o 2
minum chloride g) P4O m + H20 -> H 3P 0 4
c) M ethane gas, CH 4, bum s in air to produce car­ h) NbBrs + Nb -» NbBr 4
bon dioxide and water vapor. i) CaO + H 3P 0 4 -> Ca 3 (P 0 4)2 + H20
d) Dinitrogen pentoxide gas combines with water j) Cr 20 3 + CC14 —> СгС13 + CC120
and produces nitric acid, HNO 3 k) Mg 3B 2 + H20 —> Mg (OH )2 + B 2H 6
e) When the solutions of silver nitrate and barium 1) Ca(A10 2)2 + HC1 -4 AICI3 + C a C l 2 + H 20
chloride are mixed silver chloride and barium nitrate m) N 2H 4 + N 20 4 —> N 2 + H20
are formed n) CaC 2 + H20 -> Ca(OH )2 + C 2H 2
o) Fe 20 3 + HNO 3 -» F e(N 0 3)3 + H20
4.3 Balance the following equations and classify p) La(OH )3 4- H 2S 0 4 -4 La 2(S 0 4)3 + H20
each o f these reactions as com bination, decomposi-
' И
tion, displacement and double displacement (metathe­ 4.6 Determine the formula o f the compound repre­
sis)- А -p-, п p) sented by X in the following balanced equations
a) Al(OH )3 + HNO 3 -> A1(N0 3)3 + H20 a) 2A1(0H )3 + 3X -> A 12(S 0 4)3 + 6H20
b) Fe + 0 2 —> Fe 20 3 b) C 3H 5(OH )3 + 7 /2 0 2 -4 3 C 0 2 + 4X

t
130 Chapter 4

c) Mg 3N 2 + 6H 2O -> 2X + 3M g(OH )2 The graph given aside

d) IOHNO3 + 4Zn -> NH 4NO 3 + 3H20 + 4X shows how the mole
a)H2 S 0 4 b)H 2 0 c )N H 3 d ) Z n ( N 0 3 ) 2 numbers o f substances
change during a reac­
4.7 Find the numerical values o f x, у and z in tion.
the balanced equations a) Which are the reac­
a) CXH4 + уОг —^ 2 CO2 + ZH2O tants and which are the
b) 2BixSy + 9O 2 —^ 2Bi20 3 + ZSO2 products o f the reac­
с) 2КЙп(3,14 + xKI + 8H 2S 0 4 -> 6K 2S 0 4 + tion.
2M nS0 4 + ^ 2+ ZH2O b) What is the balanced equation with the simplest
integer coefficients ? b)3X +2Y —> Z+4R

% R E V IE W PR O B LEM S
Problem s about quantities of reactants and products

4.9 W hen PbC>2 is heated it decomposes into PbO a) Write a balanced equation for the reaction.
and O 2. Calculate the number of moles o f РЬОг re­ b) How many grams of А1(ОН)з are required to
quired for the production of react completely with 6 mol of H 2S 0 4?
a) 0.25 mol of O 2 b) 12.8 g O 2 c) How many moles of Al(OH )3 are required to
c) 2.4 x 1023 O 2 molecules d) 8.96 L O 2 produce 34.2 g Al2(S 0 4)3 ?
e) 8.2 L O 2 at 27°C and 684 mmHg d) How many grams of water are produced by the
a)0^5 b)0.8 c)0.8 d)0.8 e)0.6 reaction of 39 g А1(ОН)з with excess H 2S 0 4 ?
4.10 When propyne gas, С 3Щ , burns in air, car­ b)312 c) 0.2 d)27
bon dioxide and water are produced. 4.12 How many liters of oxygen gas at STP are
a) W rite the balanced equation representing the re­ produced from the decomposition of 9 grams of water ?
action. 54 L
b) How many moles O 2 are required to burn 0.5 4.13 Consider the balanced equation :
mol of СзН 4 ? Fe 20 3 (s) + 3CO (g) -> 2Fe + 3 C 0 2 (g) + 4.3 kcal.
c) How many moles of С зН 4 must be burned to How many liters of CO at STP are needed to release
produce 1.2 mol of CO 2 ? 8600 calories of energy in the reaction ?
d) W hat is the grams of H20 produced together 134.4 L
with 1.8 m o l o f C 0 2 ? 4.14 W hat is the volume of CI2 at 500 К and 5
e) How many grams of water are produced from 8 g atm pressure formed from 174 g o f M11O 2 by the reac­
o f C 3H 4 ? tion : МпОз + 4HC1 -> M nCl2 + 2H 2O + CI2
f)How many liters o f СзН 4 at STP must be burned 16.4 L
to produce 9 g of H 2O? 4.15 Calculate the volume o f air required to burn
g) How many liters o f С зН 4 at STP must be 2.24 L of CH 4 gas at STP according to the reaction:
burned to produce З.бхЮ 23 CO 2 molecules? CH 4 + 2 0 2 -» C 0 2 + 2H 20 . 22.4 L
h) How many grams of СзН 4 can be burned with
112 L of air at STP? 4.16 W hat is the volume, at STP, o f CO 2 and
i) How many grams of С зН 4 m ust be burned to SO 2 gases produced by the combustion of 304 mL of
produce 12.3 L CO 2 m easured at 912 mmHg and C S 2 (d= 1.25 g/mL) ? 336 L
27°C.
b)2 c)0.4 d)21.6 e ) 7 .2 f)5.6 g)4.48 h)10 i) 8 4.17 Under identical conditions, how many liters
of each of N 2 and O 2 gases must be reacted to produce
4.11 W hen А1(ОН)з reacts with H 2S 0 4 under 60 L o f N 20 3 (g) ? 6 0 L o f N 2 , 90 L o f 0 2
the proper conditions, the products are Al2(S 0 4)3
and H 2O. 4.18 Oxygen gas may be converted into ozone
 Chemical Reactions 131

gas according to the reaction 3 0 2 (g) —> 2O 3. If there ing the reaction?
is a 50 L decrease in volume of gases during the reac­ b) W hat is the mass o f’the N a H C 0 3 initially put
tion, into the test tube ?
a) what is the volume of O 3 produced? c) W hat is the mole number of Na 2C 0 3 produced?
b) what is the volume of 0 2 used? d) W hat is the total volume of the gas products at
a ) 1 0 0 L b) 15 0 L STP ? b)50.4 g c)0.3 m o l d) 13.44 L
4.19 In an experiment, a quantitiy of N aH C 0 3 is
placed into a test tube and heated. During heating the 4.20 Given the equation :
following reaction lakes place. 2NO (g) + 0 2 (g) —> 2 N 0 2 (g)
2N aH C 0 3 (s) -4 Na 2C 0 3 (s) + C 0 2 (g) + H20 (g) W hat is the volume of 0 2 at - 23°C and 1.5 atm
If the masses of the tube and its contents before necessary to react with 4.1 L of NO measured at 27°C
and after reaction are 58.45 g and 39.85 g respective­ and 684 mm Hg pressure ? W hat is the volume of
ly, answer these questions. N 0 2 at STP produced by the reaction?
a) W hat is the reason for the decrease in mass dur­ 1 .0 3 L O 2,3 .3 6 L N O 2

Problem s Involving Limiting R eagent

4.21 Given the reaction: 4.2 4 Balance the equation for the reaction o f
2NH 3 (g) +3C12 (g) -4 N 2 (g) + 6HCI (g) Mg 3N 2 with H20 to form Mg(OH )2 and NH3.What is
Determine the quantity in moles of the excess re­ the maximum number o f grams of N H 3 that can be
actant in each of the following cases.Calculate the produced from 1.00 g of Mg 3N 2 and 1.50 g of H20 ?
maximum number of moles o f HC1 for each case for 0.34 g
which the amount of reactants are given below. 4.25 How many grams of N 2F 4 can theoretically
a) 1 mol of NH 3 and 1.5 mol of Cl 2 be prepared from 17 g of N H 3 and 38 g of F 2 ? The
b) 7 mol of N H 3 and 9 mol of Cl 2 chemical equation for the reaction is : (N=14, F=19)
c) 6 x l0 22 NH 3 molecules and 2 1 x l0 22 Cl 2 mole­ 2 N H 3 + 5F 2 —4 N 2F 4 + 6HF 2 0 .8 g
cules
d) 10.2 g of NH 3 and 134.9 g of Cl 2 4.26 How many gram s of beryllium fluoride,
e)l .12 L of NH 3 at STP and 4.48 L of Cl2 at STP BeF2, can be prepared from 18 g of beryllium and 19
a) n o e x c e s s , 3 b ) l m o l N H 3 1 8 c)0.20 mol CI 2 , g of fluorine ? 2 3. 5 g
0 . 3 m o I d ) 1 m o 1 C 12 1-3 mol e)0.125 mol CI 2 ,
0.15 mol 4.27 W hat mass of M 0F 5 is obtained from 42 g
4.22 Aluminum carbide, AI4C 3, reacts with HC1 of MoFg and 66 g of Мо(СО)б by the reaction :
to produce aluminum chloride and methane gas, CH 4. 5MoF 6 + Mo(CO )6 -> 6M 0F 5 + 6CO
How many liters of CH 4 (g) at STP will be produced M oF 6 = 210, M 0F 5 = 1 9 1 , Mo(CO )6 = 264
by the reaction of 0.2 mol o f AI4C 3 with 1.2 mol of 45.84 g
HCI? 6. 72 L 4.28 Given the equation :
M n 0 2 + 4HC1 -> M nCl 2 + Cl2 (g) + 2H20
4.23 Given the skeleton equation : How many liters o f chlorine gas at STP will be pro­
FcS2 (s) + 0 2 (g) -> Fe20 3 (s) + S 0 2 (g) duced from 43.5 g of manganese dioxide and 36 .5 g of
Calculate the maximum mass of Fe 20 3 produced hydrogen chloride ? 5.6 L
when 24 g o f FcS 2 is reacted with 16.8 L of 0 2 at
STP. Which o f the two reactants is the limiting reac­ 4.29 Equal weights of calcium and oxygen gas
tant ? How much o f the excess reactant is left at the are reacted in a closed container to give 112 g of CaO.
end of reaction. FeS 2 =120 Fe 20 3 =160 Which element and how many grams will remain be­
16g, F e S 2 , 4. 48 L 0 2 hind? 48 g oxygen
132 Chapter 4

4.30 When equal weights of X and Y are reacted 4.32 Equal number of moles of iron and oxygen
to give one mole o f the compound X 2Y 3, 64 g of Y are reacted to form 32 g of iron (III) oxide. W hich ele­
remains unreacted. If the atomic weight of Y is 16 g, ment and how many grams remain behind ?
what is the atomic weight o f X ? 5 6 g/mol 3.2 g 02
4.33 Given the balanced equation
4.31 Given the equation : 3K 2M n 0 4 + 4 C 0 2 + 2H20 ->
2 S 0 2 (g) + 0 2 (g) + 2H20 (1) -> 2 H 2S 0 4 (1) 2K M n0 4 + M n 0 2 + 4X
Calculate the maximum moles of H 2SO 4 produced by Calculate the mass of X produced by the reaction
the reaction o f 4 mol of S 0 2, 2 mol o f 0 2, and 3 mol o f 6 mol of each reactant. i 600 g
o f H 20 . 3mol

P roblem s Involving Im pure S u b s ta n c e s l f

4.34 How many grams of C 0 2 are released when 4.40 How many grams o f КСЮ 3 that is 60 %
a 53 g o f N a 2C 03 sample that is 20 % pure reacts pure are required to obtain 8.2 L of oxygen at 227°C
completely with HCI ? and 1140 mmHg ? 2KC10 3 -> 2KC1 + 3 0 2 40.8 g
N a 2C 0 3 + 2HC1 -> 2NaCl + H20 + C 0 2
\ 4.4 g 4.41 How m any liters o f 0 2 at STP will be
4.35 W hen 50 g of СаСОз is heated 4.48 L of formed from 40.8 g of KCIO 3 that is 40% pure ?
C 0 2 at STP is obtained. W hat percent of СаСОз is 4.48 L
decomposed ? СаСОз CaO + C 0 2 (g) 4.42 Acetylene, C 2H 2, may be prepared in the la­
40 % boratory according to the reaction:
CaC 2 (s) + 2H20 ( 1) -> Ca(OH )2 (s) + C 2H 2 (g)
4.36 W hen 400 g of NaOH solution is reacted How many grams of calcium carbide, CaC2, that
with aluminum, 22.4 L o f H 2 gas at STP is obtained. contains 4 % impurity are required to prepare 3.36 L of
Calculate the percentage of NaOH in the solution. acetylene at STP ? 10 g
3NaOH + Al -> N a 3A 10 3 + 3/2H 2 20 %
4.43 Lead (II) nitrate decomposes into Lead (II)
4.37 W hen 600 g of iron was placed into steam, oxide and oxygen gas when heated.
the weight of the sample became 648 g. W hat percent P b (N 0 3)2 (s) -> PbO (s) + 2 N 0 2 (g) + 1/202 (g)
of the iron reacted with the steam . The reaction is : W hen 5 grams o f РЬ(Ж>з )2 was partially decom­
3Fe + 4H 20 —> Р е з 0 4 + 4H 2 21% posed, the volume of gases produced by the reaction
was found to be 307 mL measured at 27°C and 1 atm
4.38 W hen hydrogen peroxide decomposes, it re­ pressure. What percent of РЬ(МЗз )2 was decomposed ?
leases oxygen gas, according to the reaction : P b (N 0 3)2 = 331 33.1%
2H 20 2 —> 2H20 + 0 2 (g). W hat will be the loss in
weight shown by 1 kg o f a 30 % H 20 2 by w eight *4.44 Ferm antation Ц а complex chem ical pro­
sample that decomposes by 50 % ? H 20 2:34g/mol cess in which simple sugafs, СбН 120 б, are converted
71 g into ethyl alcohol, C 2H 5OH, and carbon dioxide-. Cal­
4.39 Lim estone, СаСО з, when heated , decom ­ culate the quantity of alcohol, that is 46 % pure by
poses to give CaO and C 0 2 (g). If 2.24 L o f C 0 2 gas mass, obtained from a 900 grams of glucose solution
at 27°C and 600 mmHg is obtained from 10 g of im­ containing 20 % С бН ^О б by mass. Assume the'yield
pure sample of СаСОз what is the percentage of pure of the reaction is 80 %.
С аС О з in ihe sample? 72 % 160 g
 Chemical Reactions 133

C o n s e c u tiv e R eactio ns

4.45 Potassium permanganate is prepared accord­ crafts, is prepared according to the following reactions.
ing to the following sequence of reactions in industry. 2NaOH + Cl 2 -4 NaOCl + NaCl + H 20
ЗМ п 0 2 +КС 103 +6KOH -4 3K2M n 0 4 +KC1 +3H20 NaOCl + NH 3 -> NH 2C1 + NaOH
3K2M n 0 4 + 2 C 0 2 —> 2 K M n 0 4 + M n 0 2 + 2K2C 0 3 NH 2C1 + NH 3 + NaOH -> N 2H 4 + NaCl + H20
What is the mass of K M n04 produced from 504 g of If one mole of each of NaOH, Cl2, and NH 3 are
KOH? K O H =56 K M n 0 4 =158 474 g used, calculate
a) the mass of hydrazine produced.
4.46 HNO 3 is prepared according to the follow­ b) the percentage yield o f the reaction if 8 g of
ing sequence of reactions. N 2H 4 is produced by the reaction. a)16g b ) 5 0 %
4N H 3 + 5 0 2 -4 4 N b + 6H20
NO + l/ 2 0 2 -4 N 0 2 4.48 Synthetic alcohol is produced according to
2 N 0 2 + l / 2 0 2 + H20 -> 2 H N 0 3 the reactions.
What is the maximum grams of HNO 3 produced by CaC 2 + 2H20 -4 Ca(OH )2 + C 2H 2
the reaction of 2 mol of NH 3 with 5 mol of 0 2 ? As­ C 2H 2 + H20 -> CH 3CHO
sume the excess of the other reactants. 126 g CH 3CHO + H 2 -> C 2H5OH
How many grams of С2НзОН that is 92 % pure can
4.47 Hydrazine, N 2H 4, a rocket fuel in space be obtained from 160 g CaC 2 that is 80 % pure?
j ' 100 g

S im u lta n e o u s R e a c tio n s

4.49 W hen a 50 L of a mixture of CH 4 and 4.53 A mixture of CS 2 and H2S is com pletely
C 2H 4 gases is burned, 80 L o f C 0 2 are produced at burned in an atmosphere of oxygen. The mass of S 0 2
the same conditions. Calculate the volume of CH 4 in produced is 6 times as much as that o f C 0 2. W hat is
the mixture. 20 L the mass percentage of H2S in the mixture? 49 %

4.50 "When a m ixture of 144 g of Na 2C 0 3 and 4.54 A 0.5 mol m ixture of NaCl and CaCl 2 is
N a H C 0 3 is heated, the w eight o f the mixture be­ dissolved in water and is com pletely reacted" with
comes 12.4 g less, what is the percentage of NaHCC >3 A gN 03.
in the mixture ? N a 2CC>3 is not affected by heating. NaCl(aq) + AgN 03 (aq) -4 AgCl(s) + N aN 0 3(aq)
2N aH C 0 3 -> N a 2C 0 3 + C 0 2 (g) + H20 (g) CaCl2(aq)+2AgN0 3(aq)—>2AgCl(s)+Ca(N0 3)2 (aq)
23.3 % If 340 grams of solution containing 40 % A g N 0 3 by
4.51 A 36 g mixture of Mg and Ca is reacted with mass are used in the reaction, find the mass percentage
Br 2 at high temperatures. A 212 g mixture of metal of CaCl 2 in the orginal mixture.
bromides are produced. W hat is the percentage by mass 74 %
composition of the. original mixture ? Mg=24,Ca=40 4.55 W hen 50 g of alloy of Cu and A1 react with
3 3 .3 % Mg, 6 6 . 7%Ca sufficient am ount of HC1, 22.4 L of H 2 at STP are
4.52 A m ixture consisting of CO and C 0 2 produced. W hat is the percentage of A1 in the alloy ?
weighs 7.8 g. On being oxidized with 0 2 to get com ­ Cu does not react with HC1 but A1 reacts with HC1 to
plete conversion to C 0 2, it gives a final product that produce aluminpm chloride and hydrogen gas.
weighs 11.0 g. W hat is the mole ratio of CO to C 0 2 36 %
in the orginal mixture ? 411
134 Chapter 4

4.56 C u20 and CuO may be converted into cop­ 4 .57 W hen a 6.1 g mixture o f СаСОз and
per by the reactions. ЫаНСОз is heated 2.31 g o f C 0 2 and 0.225 g of H20
C u20 + H 2 -> 2Cu + H20 are produced according to the reactions.
CuO + H 2 -> Cu + H20 C a C 0 3 -> CaO + C 0 2
If 80 g of Cu is obtained from 96 g mixture of 2N aH C 0 3 -> Na 2C 0 3 + C 0 2 + H20
copper oxides, find the percentage by mass of CuO in Find the mass o f СаСОз in the mixture. 4g
the mixture. Cu=64 62.5%

E m pirical Form ula D e te rm in a tio n s

4.58 Determine the empirical formula of the com­ and some quantity of oxygen. W hat is the empirical
pounds made of only С and H in each of the following formula of the new oxide ? M n30 4
a) The combustion of 0.4 mol o f compound pro­
duces 0.8 mol of C 0 2 and 1.2 mol of H20 4.63 A compound known to contain only P and S
b) The com bustion o f a quantity of compound was analyzed by converting all o f P atoms into 4.44 g
produces 33 g of C 0 2 and 18 g of H20 of Mg 2P 20 7 and all of S atoms into 23.3 g B aS 0 4.
c) The combustion o f 4 g of compound produces Calculate the empirical formula of the compound.
6.72 L of C 0 2 at STP P2S5
d) The mass of H20 is 0.45 times the mass of 4.64 The combustion of 2.9 g of compound con­
C 0 2 in the combustion products of the compound. taining С and H produces 4.48 L C 0 2 at STP. The
a ) C 2 H 6 b )C3 H 8 c) C3 H 4 d ) C5H u density of the vapor o f this compound is 0.59 g/L at
0.25 atm and 27°C. W hat is the molecular formula of
4 .5 9 The com plete com bustion o f a 18.5 g of the com pound ? C4H 10
compound consisting of С, H and О produced 44 g of
C 0 2 and 22.5 g of H 20 . W hat is the empirical formu­ 4.65 A sam ple o f com pound decom poses into
la of the compound? C4 H 20 O 24.32 g Cr 20 3, 3584 mL of N 2 at STP, and 11.52 g
of H 20 . Determine the empirical formula o f the com ­
4.60 W hen a quantity of compound containing C, pound. (N H 4 ) 2 C r20 7
H and S is com pletely burned in oxygen, 88 g of
C 0 2, 18 g of H20 and 32 g of S 0 2 are produced. *4.66 The combustion products of a compound of
a) Calculate the mass of the compound that is С, H, О and N elements has the following percentage
burned. compositon by mass. 59.9 % C 0 2, 9.5 % N 2 and 30.6
b) W hat is its empirical formula ? 42 ^ ,€ 4 1 1 4 8 % H 20 . The mass of 0 2 required for burning a quanti­
ty of the substance is equal to the mass o f C 0 2 pro­
4.61 When 0.01 mol of a compound containing duced. If the molecular weight of the compound is 59
only С, H and О is burned, 0.72 g of H20 and 896 g/mol, find the molecular formula of the compound.
mL of C 0 2 measured at STP are produced. If the com­ C2H 5N ()
pound contains 14 atoms per molecule, what is the * *4.67 1 mol of com pound containing only С
molecular formula of the compound? and H is completely burned to give C 0 2 and H 20 . The
c4H8o2 analysis of the combustion products shows that the
mass of the products is 160 g larger than the mass of 1
4.62 When a 13.05 g sample of M n 0 2 is healed it mol of the compound and the mass o f C 0 2 is 60 g
decomposes to give 11.45 g of another oxide of Mn larger than the mass o f H 20 . Determine the molecular
formula of the compound. (C=12, H = l,0 = 1 6 ) C3 H 8
 Chemical Reactions 135

A tom ic And M olecular W eig ht D eterm inatio ns

4.68 Calculate the atomic weight o f the element 4.72 The sulfur dioxide gas obtained from the
represented by X in each of the following. combustion of 6.4 g of sulfur is used in the following
a) 10.8 g A1 combines with 32 g X 2O 3 according reaction. 4 M + S 0 2 -» 2M20 + S. If 24.8 g of M 20
to the equation 2A1 (s) + Х 20 з (s) —> А120 з + 2X (s) is produced in the reaction, find the atomic weight of
b) 2.24 L X 0 2 at STP is produced from 3.8 g of M. 2 3 g/mol
CX 2 in the equation: *4.73 W hen M 2S 3 (s) is heated in air, it is con­
CX 2 (1) + 3 0 2 (g) -> C 0 2 (g) + 2 X 0 2 (g) verted to M 0 2 (s) and S 0 2. If a 20 g sample of M 2S 3
c) 26 g of XC12 is produced from 37 g of XBr 2 in shows a decrease in weight of 3.2 g, what is the atom ­
the equation XBr 2 (s) + Cl 2 (g) —> X C b (g) + Br 2 (1) ic weight of M ? S=32 0 = 1 6 52 g/mol
d) 27 g of XCI3 is produced from 11.2 L HC1 at
STP in the reaction : 4 .7 4 When 4 g of XBr 2 react w ith sufficient
2X (s) + 6HC1 (g) 2XC13 (s) + 3H 2 (g) amount o f AgN 0 3 , 7.54 g of AgBr are formed. W hat
a )56 b)32 c )1 3 9 d)55.5 is the atomic weight of X ? 40gtmol

4.69 Calculate the atomic weights of X and Y ele­ *4.75 78 g of chromium react com pletely with
ments in each of the following. the element X to give Сг2Хз. All o f the X in Сг2Хз is
a) 30 g оР Х зУ 2 combines with 10.8 g of H20 to treated with barium to produce BaX. All the BaX
produce 17.4 g of X(OH )2 and some YH 3. formed is reacted with excess potassium and all of the
b) 11.2 L of X 0 2 (g) at STP reacts with 52 g of element X in BaX is changed into K2X. If the mass of
YO (s) to give 74 g of XYO 3 and some water. K2X formed is 247.5 g, what is the atomic weight of
c) 16.2 g of X (s) combines with 12.6 g of HYO 3 X ? Cr= 52,K= 39 32glmol
to produce 1120 mL of YO (g) at STP.
3X + 4 H Y 0 3 3 X Y 0 3 + YO + 2H20 *4.76 When 1.51 g sample of pure and dry M XO 3
■a) X=24, Y=14 b)X=I2, Y=88 c)X=108, Y=14 is heated, 0.48 g of 0 2 and 1.03 g of MX are formed
as products. All the MX formed is reacted with excess
4.70 Given the equation: AgN 03 to form 1.88 g of AgX. If the atomic weights
ЗА (s) + 8B (s) 2C (g) + 3D (s) + 2E (s) of oxygen and silver are 16 and 108 r e s ^ . tively, what
If the complete reaction of 48 g of A with 126 g of arc the atomic weights of M and X ? M =23, X = 8 0
В produces 11.2 L of С (g) at STP, what are the mo­
lecular weights of A and В ? 6 4 g / mo l , 6 3 g / m o l *4.77 In the decompositon o f 26.28 g of
M (X 0 3)2, MX 2 and 7.872 L of 0 2 at 570 mmHg and
4.71 W hen 13.35 g of MYO 3 is heated, until no 127°C are produced. If all the MX 2 produced is reacted
more gas is produced, 11.15 g o f MO (s) and 1.12 L with excess chlorine' gas, Cl2 to form 9.54 g MC12,
of Y 0 2 gas at STP are produced. Calculate the atomic what are the atomic weights of M and X ? О =16,
weights o f M and Y elem ents. 2 0 7 g / m o l , 1 2 g l m o l Cl = 35.5 M =8 8 , X = 1 27

C ollecting G ases O ver W ater

4.78 Mg + 2HC1 M gCl 2 + H 2 (g) 4.79 A 1 g impure sample of Zn is used to collect

How many grams of Mg are required to collect 50 mL 246 mL of H2 gas over water at 23°C and 783 mmHg.
of H2 gas over water at 20°C and 754 mmHg ? Calculate the percentage of Zn in the sample.
- ISm m Hg at 20°C P 112o = 23mmHg at 23PC
0.048 g 65 %
136 Chapter' 4

4.80 Hydrides of alkali metals (NaH,KH,....) react 4.81 100 mL of 0 2 gas is collected over water at
with water to produce metal hydroxide and hydrogen 764 mmHg pressure and at 25°C. Рц2о = 24 mmHg.
gas. If 50 mL of H 2 (g) is collected over water at 17°C a) Calculate the mass of 0 2 collected.
and at a total pressure of 764 mmHg, calculate the b) How many grams of КСЮ 3 are needed to pro­
amount of KH used. If NaH were used instead of KH, duce this quantity of oxygen?
what mass of NaH would have required ? a)0.13 g b)0.33 g
P h 20 = 14 mmHg 83 mg, 5 0 m g

P ressure C han g e s In R eactions

*4.82 0.4 mol o f C 3H 4 (g) and a quantity of 0 2 4.87 W hen 30.4 g N 2H 6C 0 2 (s) is heated in a
that is just enough to burn 0.4 mol of C 3H 4 are placed 8.2 L container at 177°C, it partially decomposes to
in a 8.2 L container at 27°C. W hen an electric spark is N H 3 (g) and C 0 2 (g) developing a pressure of 4.05
passed through the mixture C 3H 4 burns completely atm. What is the mass of N 2H 6C 0 2 (s) remained unde­
and temperature rises to 127°C. Calculate the pressure composed ? 7 g
in the container at the end of reaction. 8 atm
*4.88 A 4.92 L contanier has He (g) and H20 (1)
4.83 One method for preparing N 2 (g) is the ther­ at 27°C. The pressure in the container is measured as
mal decomposition of sodium azide, N aN 3, by the re­ 787 mmHg. The water is then completely electrolyzed.
action : NaN 3 (s) —> Na (s) + 3/2N 2 (g) W hat pres­ After the completion o f the reaction, the pressure is
sure will be developed by the complete decomposition 2.5 atm at the same temperature. W hat mass of water
of 13 g of NaN 3 in a 4. 1 L container at 77°C ? was in the container ? Р н 2о at 20 °C = 27 torr 3. 6 g
Na=23, N=14 2.1 atm
*4.89 A container holds 0.2 mol of N 2 and 0.3
**4.84 A 1 L steel bomb contains sulfur trioxide mol of H 2 at STP conditions. W hen the container is
at 227°C and 16.4 aun. If the temperature is raised to heated to 273°C, NH 3 is formed by the reaction :
727°C, the pressure increases to 36.9 atm because of N 2 (g) + 3H 2 (g) -> 2NH 3 (g)
the reaction: 2 S 0 3 —> 2 S 0 2 + 0 2 W hat is the per­ After the completion of the reaction calculate
cent decomposition by mass of sulfur trioxide ? a) the total pressure.
25 % b) the partial pressure of each gas in the container.
*4.85 A 20~liier container is full of air which is a ) 1 .2 a t m b ) P i y 2 ~ 0 .4 a t m Р/ у j [ j = 0 . 8 a t m
20 % oxygen and 80 % nitrogen. A sample of carbon 4.90 At a certain temperature, a closed container
is added to the container and the temperature is raised has 14 g of N 2, 1 mol o f 0 2, and 2 g of H 2 gases.
to 427°C. All of the carbon and oxygen are used up in The total pressure in the container is 2.5 atm. When
the reaction and 1/3 of carbon changes into CO and an electric spark is passed through the mixture, the liq­
2/3 of С into C 0 2. After the reaction stops, the pres­ uid water forms and then the container is cooled to the
sure in the container at 427°C is 18.655 atm. W hat is original temperature. W hat will be the total pressure ?
the mass of carbon added to the container ? 18 g P h 90 = 25mmHg 785 m m H g

4.86 W hen 25 g N H 4C1 (s) is heated in a closed 4.91 The thermal decom position o f silver carbo­
vessel at 177°C, 85.6 % by mass of NH 4C1 decom ­ nate, Ag 2C 03 (s) produces Ag (s), C 0 2 (g) and 0 2. If
poses into N H 3 (g) and HCI (g). The total pressure is the partial decomposition of 46 g of Ag 2CC>3 produced
measured 4.5 atm after the reaction. Calculate 3 L of C 0 2 measured at 27°C and 623.2 mmHg, cal­
a) the volume of the continer culate the percentage by mass of Ag 2C 03 that h;'°-- ’
b) the partial pressures of NH 3 and HCI composed. Ag 2CC>3 =276 g/mol
6.56 L, 2.25 atm each.
 Chemical Reactions 137

M is c e lla n e o u s P ro b lem s
4.92 The H 2 gas produced by the reaction o f a 4.97 It was formerly believed that organic com ­
quantity of A1 with 500 g of H 2SO 4 solution is com ­ pounds (the compounds in living organisms) were ex­
pletely used in the reaction: clusively of plant or animal origin. In 1828 Friedrich
CuO + H 2 -> Cu + H20 Wohler, a German chemist, reported the preparation of
If 144 g of Cu is obtained, what is the mass percent­ the first organic compound, urea, (NH 2) 2CO, in labor­
age of H 2SO 4 in the H 2SO 4 solution? Al=27, Cu=64 atory according to the reactions :
44.1% I. KCN + P b 0 2 -> KCNO + PbO
*4.93 A 8.2 L container holds 4 g o f H2, 0.5 II. 2KCNO + (NH 4) 2S 0 4 2NH4CNO + K 2S 0 4
mol of 0 2 and some N e gas that exerts a pressure o f 2 III. NH4CNO -> (NH2)2CO
atm at 127°C How many grams o f urea can be prepared from 100 g
a) How many moles of gas are there in the container ? quantities of each of the necessary substances. Assume
b) W hat are the total pressure and partial pressure of the yield o f the overall reaction is 60 %. 15.l g
each gas ?
c) If a spark is passed through the m ixture and the 4.98 A mixture o f 5 mol of N 2 and C 0 2 gases
temperature is held 127°C, what will be the total pres­ which exert 2 atm pressure is passed through 200 g
sure in the container ? 74% by weight of Ca(OH ) 2 solution and all the C 0 2
a)3 b)Pj=12atm P q 2 = P ^ e=2atm c)10atm is absorbed by the solution. W hat was the partial pres­
*4.94 W ater gas, an industrial fuel, is obtained sure of CO 2 in the original mixture ?
by the action of. steam on glowing hot coke, giving C a(O H )2 + C 0 2 —> СаСОз T H 2C 0 .8 at m
carbon monoxide and hydrogen gases. When it burns it
produces C 0 2 (g) and H20 (g) as well as 2500 kcal of *4.99 A sample of aluminum reacts with excess
energy per m 3 at STP water gas burned. hydrogen chloride to give hydrogen gas. The gas pro­
a) W hat is the maximum volume in m 3 of water duced is introduced into a tank that already contains
gas at STP that can be produced from 1 tone of coke 67.2 L o f methane gas C H 4, at 27°C and 1.64 atm.
(96 % С by mass) and 8.2 m 3 of steam at 1000 К and After introducing H 2, into the tank, the temperature
1 atm? rises to 155°C and the partial pressure of hydrogen is
b) How many kcal of energy will be produced from the same as the partial pressure o f methane. W hat is
the combustion of this water gas at STP? the mass of aluminum reacted with HC1 ? A1 = 27
a )4.48m 3 b)11200 kcal 8 0.64 g

4.95 Sr(XC>3)2 (s) decomposes into SrX 2 (s) and

0 2 (g) when heated. The volume of gas obtained by 4.100 A mixture of СаСОз apd N aH C 03 is 44%
decom posing 10.95 g o f Sr(XC>3)2 is 2.46 L at 950 СаСОз by mass. The thermal decomposition of this
torr and 227°C. Calculate the atomic weight of X. mixture produces 0.9 g of H 20 .
127 g/mol СаСОз (s) -> CaO (s) + C 0 2 (g)
4.96 16.8 L of 0 2 at STP are needed to burn 0.25 2N aH C 0 3 -> Na 2C 0 3 (s) + C 0 2 (g) + H20 (g)
mol of a compound. If the com bustion products are a) what is the mass of the mixture decomposed ?
11.2 L C 0 2 at STP and 0.75 mol of H 20 , find the b) what is the volume of C 0 2 at STP produced by
molecular formula of the compound. the mixture ?
c 2H 6o 15g ,2 .6 0 L
138 Chapter 4

SELF TEST

1. In chemical reactions, 7. X (OH) 2 + 2HC1 -> XC12 + 2H20

1. atoms are always conserved. W hen 0.4 mol of HCI is used in the given reaction, 19
II. volumes are always conserved. g of XC12 is produced. W hat is the atomic weight of
III. mass is always conserved. X ? (Cl = 35.5)
IV. number o f molecules is always conserved. A) 95 B) 59.5 C) 47.5 D) 24 E) 19
Which ones o f the statements given above are
CORRECT ?
A) I - III В) I - II - III С) II - III 8 . How many liters o f N H 3 (g) at 0.82 atm and
D) III - IV E) II - III - IV 27°C will be formed when 7 g of Li3N reacts with wa­
ter according to the reaction : Li=7, N=14
2. Which o f the following compounds is repre­
Li3N (s) + ЗН 2О (1) -> 3LiOH (aq) + NH 3 (g)
sented by X in the balanced equation :
X + 12H20 -> 4A1(0H )3 + ЗСН4 A) 6 B) 5 C) 4 D) 3 E) 2
A) A120 3 B) AIH3 C) AI4C 3
D) A1(HC03)3 E) A12(C 0 3)3 9. If 2.8 g of CO and 3.2 g o f 0 2 are mixed and re­
acted to give C 0 2, how many grams of C 0 2 can be
3. CO (g) + l / 2 0 2 (g) -> CO, (g) + 67.6 kcal. produced at most ? C = 1 2 ,0 = 1 6
If 56 g of CO is used in the reaction above, which one A) 6.0 B) 4.4 C) 3.6 D) 3.2 E) 2.8
o f the following will be true ? ( С = 12, О = 16 )
A) 1 mol of C 0 2 is produced. 10. A reaction is started with equal weights of Al
B) 67.6 Kcal of heat is released a n d 0 2, and 0.5 mol of A120 3 is produced. Which ele­
C) 0.5 mol of oxygen is used. ment and how many grams remain behind? Al2O 3=102
A) 9 g Al B) 3 g Al C) 3 g 0 2 D) 6 g 0 2 E) 9g 0 2
D) 0.5 mol of C 0 2 is produced.
E) 1 mol 0 2 is used.
11. A 100 liter o f a mixture of N 2 and H 2 gases is
4. Consider the following reaction : reacted to give NH3. If 20 liters of N 2 remains unreact­
N aH C 0 3 + HCI -> NaCl + H20 + C 0 2 ed, how many liters of N H 3 will be produced at most ?
Calculate the volume in liters of C 0 2 at 27 °C and A) 80 B) 60 C) 40 D) 30 E) 20
380 mmHg pressure when 2 1 g of N aH C 0 3 reacts
with excess HCI ? N aH C 0 3 =84 g/mol 12. The com bustion of 0.25 mol o f com pound
A) 2.46 B) 1.23 C) 1.02 D) 0.62 E )0.31 containing С, H, and О requires 1.25 mol o f 0 2, and
produces 1 mol of C 0 2 and 1 mol o f H 20 . W hich is
the molecular formula of the compound ?
5. When 5.6 g of A reacts with 9.6 g of B, 4.48 L
A) CH20 В) C 4H 4O C) C 4H 60 2
of С at STP are formed. What is the molecular weight
D) C 4H 80 2 E) C 5H 80 3
of С ?
A) 30 B) 38 vC) 76 D) 108 E) 152
13. The combustion o f 12 g of a compound made
from С, H and О produced 8.96 L o f C 0 2 at STP and
6 . 1.12 L of C 0 2 gas at STP is obtained by heat­
7.2 g of H 20 . W hich was the simplest formula of the
ing 20 g o f C a C 0 3. What percent o f C a C 0 3
compound burned ?
(MW=100 g/mol) was decomposed according to the
A) CH20 B) C 2H 6 C) C 2H 50 2
following reaction ? C aC 0 3 —> CaO + C 0 2
D) C 3H 60 2 E) C 3H 70 2
A) 5 B) 10 C) 15 D) 20 vE) 25
 Chemical Reactions 139

14. The reaction o f 6 mol of H 2 with 1.5 mol of at room temperature. If the mixture is ignited with an
N 2 produces 2.4 mol of NH 3 according to the follow­ electric spark and then cooled to the room temperature,
ing reaction: 3H 2 + N 2 2 NH 3 what will be the pressure in mmHg ?
Which is the percent yield o f the reaction ?' (P h 2o = 23 mmHg.)
A) 40 B) 50 C) 60 D) 70 E) 80
A) 200 B) 223 C) 227 D) 300 E) 323

15. A portion of n mol sample o f Y 2 reacts with

2 mol of X 2 to give 2 mol o f X2Y and the remaining 19. The mixture of 0.6 mol o f N 2 and 0.6 mol of
part of Y 2 com bines with 1 mol of Z to form 1 mol H 2 gases are reacted to give N H 3 gas. The reaction oc­
* of ZY. W hat was the mole number of Y 2 initially? curs in a closed container. The pressure and tem pera­
ture are 720 mmHg and 27°C before the reaction. If
A) 0.5 В) 1 C) 1.5 D) 2 E) 2.5
temperature is increased to 127°C, what will be the
16. W hen 5 mol mixture of С and S elements are pressure in mmHg in the container after the com ple­
burned, 260 g mixture of C 0 2 and S 0 2 are produced. tion of the reaction ?
W hich is the mass percentage of С in the mixture ? A) 960 B) 640 C) 480 D) 320 E) 280
C=12, S=32, 0 = 1 6
A) 12 % B) 24 % C) 36 % D) 48 % E) 64 % 20. Sulfuric acid, H 2S 0 4, may be prepared by the
с
с Q
following sequence of reactions:
17. In a gas m ixture the mole ratio of C 2H 4 to S g + 8 0 2 —> 8 S 0 2
C 3H 8 is 1/2. To burn 15 liters of the mixture, how 2 S 0 2 + 0 2 —6 2 SO 3
many liters of 0 2 arc needed at the same conditions ? S 0 3 + H20 H 2S 0 4
A) 8 B) 13 C) 26 D) 45 E) 65 W hat mass of H 2S 0 4 will be produced from 100 g
sample that is 96 % sulfur by mass ? S=32, 0 = 1 6 ,
18. A container has 0.1 mol of H 2, 0.1 mol of 0 2 H=1
and 0.1 mol of He and the total pressure is 600 mmHg A) 98 g B) 196 g C) 294 g D) 490 g E) 588 g
 CHAPTER

Condensed Phases of Matter :

Liquids and Solids

The objectives of this chapter are to enable the student to :

1.Apply the kinetic m olecular theory to a differentiation of the
properties of gases, liquids and solids.
2.Define the normal melting point and the molar heat of fusion.
3.Define the vaporization and the molar heat of vaporization.
4.Describe the condition of dynamic equilibrium between a liquid
and its vapor.
5.Define the boiling point.
6 .Define solute, solvent, solution.
7.Explain the types of solutions.
8 .Explain the differences between solutions and pure substan­
ces.
9.Express the concentration of a solution by means of molarity
and percentage by mass.
lO.Define molarity and normality and calculations for each of them.
11.Identify the solubility.
12.Explain how to separate solutions into components.
13.Recognize the electrical nature of matter.
14.Explain the behavior of ionic and molecular solids in solutions.
15.Calculate the concentrations of ions in solutions.
16.Recognize the precipitation reactions in solutions.
 Condensed Phases o f M atter Liquids and Solids 143

M o st o f th e su b stan ces w e see around us are so lid s. S o m e are liq u id s

and a very few are gases. W hen the tem perature is low ered, the m o lecu les o f a
g as slo w d o w n and the g as c o n d en ses to a liq u id . In liq u id s, m o le c u le s are
very clo se to each other. T he m olecules m ove very slow ly. T h e intcrm o lecu lar
a ttractiv e forces are able to hold the m o lecu les o f liquids to g e th e r into a d e fi­
nite volum e. T h erefore a liquid flow s and takes the shape o f any con tain er into
w h ich it is put. W hen the tem perature o f a liquid is d ecreased, the average k i­
n etic energy o f the m olecules decreases and then a solid form s. T h e m o lecules
in th e so lid o c c u p y a reg u la r p o sitio n , o r w e m a y say th a t so lid s are rigid.
T h e se and o th e r p ro p e rties o f liquids and solids can be e x p la in ed in term s o f
the kin etic m o lecu lar theory o f m atter, w hich w e used to e x p lain the properties
o f gases.
T h e se p ara tio n b etw e e n the m o le cu les o f so lid s and liq u id s e x tre m e ly
sm all co m p ared to the distan ces betw een gas m olecules. T h erefo re solids and
liq u id s are called cond en sed phases o f m atter. In this ch a p te r w e w ill exam ine
the p ro p erties o f condensed phases o f m atter, solids, liquids, and solutions.

5.1 PHASE CHANGES

5.1.1 M ELTIN G AND H E A T OF M ELTIN G
W hen a solid is h eated the k in etic energy o f its atom s, io n s o r m o lecu les
(th e stru ctu ral u n its) in creases and solid w arm s. T he q u a n tity o f h e a t en ergy
necessary to change the tem perature o f one gram o f substance by 1 °C is called
the sp e c ific h e a t o f the su b sta n c e , a n d re p re se n te d by c. Its u n it is e ith e r
cal/g°C o r J/g°C. T h e quantity o f h eat necessary to w arm m gram o f substance
from ti°C to t 2°C m ay be calculated by the form ula.
Q uantity o f heat = m ass x specific heat x tem perature change

or f q(cal) = m (g) x с ( ^ - ) * Д t C q ]

If the tem perature is great enough, the m olecules m ay overcom e the in tcr­
m o le c u la r forces holding them to gether in th eir fixed positions, and the regular
c ry sta l p a tte rn o f th e so lid is d estro y e d . T h is is called m e ltin g o r fu s io n .
D u rin g m eltin g , so lid and liquid ph ases o f the sam e m atter coexist. The tem ­
p e ra tu re a t w h ich the so lid a n d liq u id sta te s o f a su b sta n ce ex ist to g e th e r is
ca lled the m elting p o in t (m .p). E ven though heating is continued, the tem p era­
ture rem ains constant at the m elting point until all the solid has m clted.T he heat
su p p lied to the m eltin g solid is used fo r in c re a sin g the k in e tic en erg y o f the
stru ctu ral u n its o f the so lid .The q u a n tity o f h e a t n e e d e d to ch a n g e 1 m o l o f
s o lid in to the liq u id a t the m e ltin g te m p era tu re is ca lle d the m o la r h e a t o f
m e ltin g o r m o la r h e a t o f fu s io n .F o r e x am p le th e m o la r h e a t o f fu sio n o f
ice is 1.44 kcal.
H 20 (s) + 1.44 kcal -> H 20 (1) (at 0°C)

B u t it is m ore p ra ctica l to ex p ress the h e a t o f fu sio n p e r g ram o f su b ­

stan ce m elted . In th at case th is e n erg y is called la te n t h e a t o f fu s io n (a b ­
b reviated Lf). F o r w ater, the latent h eat o f fusion is 80 cal/g.
 144 Chapter 5

( . 1 : 4 1 b ? 1 = 1440ca l = 8 ()c a l/ )
1 mol H 20 18 g

The quantity o f energy needed to m elt m gram o f substance at its m .p

m ay be calculated by using the formula :
( q ( c a l) = m (g ) x L f ( c a l / g f )
The reverse process o f m elting, the conversion o f a liquid to a solid, is
called freezing. The m elting temperature (m.p) and freezing temperature (f.p)
o f a pure substance are the sam e. W hen a liquid freezes the heat o f fusion is
giv en off. h 20 (1) - » H20 (s) + 1.44 kcal (at 0°C)
The m elting temperatures and the molar heats o f som e com m on substanc­
es are given in Table 5 .1
TABLE 5.1 H ea ts o f fu s io n a n d vaporization o f som e substances.
>
S u b sta n c e m .p. (° C ) H eat o f Fusion (k cal/m o l) b .p (°C ) H e at o f V a p o raz itio n (k c al/m o l)
N eo n - 2 4 8 .4 0 .0 8 -2 4 5 .8 0 .4 0 5
A rg o n - 189 0 .3 0 -1 8 6 1 .5 9
C h lo rin e - 101 1 .5 3 -34.1 4 .8 8
C a rb o n d isu lfid e - 11 2.1 1 .0 5 46.3 6 .4 0
E thyl a lc o h o l - 117.2 1 .1 0 61.3 7 .0 3
C h lo ro fo rm - 63.5 2 .2 0 76.7 7 .1 7
C a rb o n te tra c h lo rid e - 2 2.9 0 .6 0 78.5 9 .2 3
B e n ze n e 5 .5 2 .3 4 80.1 7 .3 1
W ater 0 1 .4 4 100 9 .7 2
Sodium 98 0 .6 3 889 2 4 .1
S odium ch lo rid e 808 6 .8 0 1465 4 0 .8
i^Copper 1083 3 .1 1 2582 72.8
J
A grapich representation o f temperature versus tim e o f heating is show n
in Fgure 5.1 for water.

FIGURE 5.1 H e a tin g c u r v e fo r w ater. W h e n

ice a t -1 0 °С is h e a te d th e te m p e ra tu re in c r e a se s
until th e m eltin g p o in t is re a c h e d . T h e te m p e ra ­
ture rem a in s c o n s ta n t a t th e m eltin g p o in t (0°C )
until all o f th e ice is m e lted . A fte r all th e ic e h a s
m e lte d th e te m p e ra tu re o f th e w a te r b e g in s to in ­
c r e a s e again.

EX A M P LE 5 .1 F in d in g H e a t o f M e ltin g
Problem : How much heat is needed to melt 36 g o f ice at 0°C ?
Solution : Molar heat o f melting of ice is 1.44 kcal. To melt one mole of ice at 0°C, 1.44 kcal are needed.
Then, to melt 36 g (36/18 = 2 mol) o f ice, 2 mol x 1.44 kcal/mol = 2.88 kcal are needed.
Or q = m x Lf = 36 g x 80 cal/g = 2880 cal => 2.88 kcal
 Condensed Phases o f M atter Liquids and Solids 145

EXAM PLE 5.2 Finding the Heat Necessary in Phase Change

Problem : How many calories are required to change 9g of ice at -20°C to water at 0°C ?
Solution : The initial temperature of ice is - 20°C. When it is heated, its temperature will increase to 0 °C
(melting point) and then it will melt. qt q2
Ice at - 2 0 ° C —» ice at 0 °C —> water at 0 °C
°c
q, = m x с x At
q ( = (9g) x (0.5 cal/g °C) x (20 °C) = 90 calories
q q 2 = m x L f = 9 g x 8 0 cal/g = 720 cal
S ' H eat added qtotal = q, + q2 = 9 0 + 7 2 0 = 8 1 0 c a lo r ie s
(h e a tin g tim e )
-20 / q ,

EXER C ISE 5.1 How many calorics arc required to melt 5.00 g of ice at 0°C and raise the temperature of
the resulting water to 35°C ? 575 cal

EXER C ISE 5.2 Calculate the quantity of heat released when 50 g o f water at 80°C is converted to ice at
-20°C . 8500 cal

E X A M P L E 5.3 F in d in g H e a t R e la tio n in P h a se C h a n g e
Problem : When 5.85 g of sodium chloride is solidified, 680 calories of heat arc released. Calculate the m o­
lar heat of solidification o f sodium chloride. NaCl = 58.5 g/mol
Solution : The molar heat o f solidification of sodium chloride is the quantity of heat released when 1 mol or
58.5 g of liquid sodium chloride freezes.
nxaCl = 5.85/58.5 = 0.1 mol
If 0.1 mol of NaCl releases 680 calorics
, г. т , I x = 6800 calories = 6.8 kcal/mol
1 mol of NaCl releases____________ x____ J

9
5 .1.2 E V A P O R A TIO N A ND H E A T O F E V A P O R A TIO N
In liq u id s, the m o le cu le s m o v e m o re slow ly th a n th e y do in gases. T h e
in te rm o le c u la r attractive fo rces are able to h o ld them to g e th e r into a d efinite
volum e. A m olecule in the center o f a liquid is attracted'equally in all directions
b y th e su rro u n d in g m olecules. M o lecu les o n the surface o f a liq u id , h o w ever,

• ^■ L M v— M are attracted only tow ard the in terior o f the liquid. S ee F igure 5.2
T h e surface tension o r the attractio n b e tw e e n th e m o lecu les o f a liq u id
o n th e su rface decreases w ith in creasin g the tem perature. In crea sin g th e tem ­
peratu re in creases th e kinetic energy o f m olecules. T he m o lecules w ith k in etic
FIGURE 5.2 T h e m o le - e n e rg ie s h ig h en o u g h to o v erco m e th e attractiv e fo rces can e sca p e fro m the
c u le in th e interior ex p e ri- liquid. S o o n the liq u id boils. F o r ex am p le, w a te r b o ils a t 100°C and th e tem -
e n c e s e q u a l a ttr a c tiv e p eratu re stays co n stan t as long as liquid w ater rem ains.
fo r c e s from all d irectio n s. „ TT _ , .
B u t th e re is a n im b a la n c e H 2° ^ q u i d ) + en ergy -> H 20 (vapor)
o f fo rces o n a m o le c u le a t Gr H 20 (1) + 9.72 k c a l -> H 20 (g)
th e su rfa c e o f a liquid.
146 Chapter 5

F ig u re 5.3 show s th a t addition o f en ergy at 100°C does n o t increase the

tem p eratu re. T h e k in etic en erg y added to the liquid w a ter du rin g b o iling
causes th e m olecules to separate from each other. It is stored as potential
en erg y in th e separated gas m o lecules. T he a m o u n t o f h e a t req u ired to
e va p o ra te o n e m o le o f liq u id a t its b.p. is c a lle d the m o la r h e a t o f
v a p o riza tio n . T h e m o la r h eat o f v a p o riza tio n o r e v ap o ratio n fo r w ater
at 100°C is 9.72 kilocalories. The h ea t o f va p orization p e r gram o f su b ­
F I G U R E 5 . 3 H e a tin g c u r v e sta n ce is c a lled the laten t h ea t o f v a p o riza tio n , L v. It is 54 0 cal/g fo r
fo r w ater. T h e te m p e r a tu r e o f w ater. W h en w ater v a p o r condenses to liquid w ater, the p o ten tial energy
the w a ter in c r e a s e s until 100°C. is released in the form o f heat energy.
It re m a in s a t 1 0 0 °C until all o f H 20 ( g ) ----------- -> H 20 (1) + 9.72 kcal
w a te r e v a p o r a te s . L a te r th e T h e bo ilin g tem perature and h eat o f v ap o rizatio n fo r v ario u s are
te m p era tu re o f va p o r in c re a se s. listed in T able 5.1, and the term s ab o u t phase ch an g es arc su m m a r­
ized in Figure 5.4

F IG U R E 5 . 4 The possible phase changes and the terms related to them. Sublimation is a direct transition of a
solid into vapor. The reverse of sublimation is deposition. Naphthalene and iodine are two common substances
that sublime when heated.

E X A M P L E 5.4 M o la r H ea t o f V a p o r iz a tio n
Problem : How many calorics arc needed to vaporize 1080 g of water at the boiling point?
Solution : ti[| 0 = 1080 g/18 g/mol = 60 mol
Molar heat o f vaporization o f water at the boiling point is 9.72 kcal. Then, the amount o f heat required to evapo­
rate 60 mol o f water is: 60 mol x 9.72 kcal/mol = 583.2 kcal
Instead of molar heat of vaporization we can use the latent heat of vaporization of water as 540 cal/g. In that
c ase: q = m x Lv => q = ( 1080 g ) x (5 4 0 cal/g) = 583200 cal= 583.2 kcal

E X A M P L E 5 .5 F in d in g H ea t A c c o m p a n y in g P h a se C h a n g e s
Problem : Calculate the number of calories required to melt 20.0 grams of ice at 0°C and convert the result­
ing water to steam at 100°C.
Solution : We know that this involves three changes, 1. converting the 20.0
grams of ice to water al 0°C, 2. raising the temperature of the water to 100°C, 3. con­
100
verting the water to steam at that temperature. The sum of the quantities of heat re­
quired in these three changes gives us the answer.
20 g ice at 0°C -» 20 g water at 0°C —> 20 g water al 100°C -» 20 g vapor at 100°C
H eat added
 Condensed Phases o f M atter Liquids and Solids 147

qj = m x Lf = (20.0 g) x (80 cal/g) = 1600 cal

q 2 = m x с x At = (20.0 g) x (1 cal/g°C) x (100°C) = 2000 cal
q 3 = m x L v = (20.0 g x 540 cal/g) = 10800 cal } J- qlola) = 4 l + q 2 + q3 = 14400 cal

EXERCISE 5.3 How many calorics arc required to transform 10 g of icc at - 10 °C to vapor at 110 °C ?
7300 cal

E X A M P L E 5.6 Finding Final Temperature, Using Heat Relation in Phase Changes

Problem : If 4000 calories are given to 40 grams of ice at - 20°C , what will be the final temperature and
the physical state ?
Solution : W hen some amount of heat is given to ice, first its temperature will raise to 0°C and it will melt,
and then its temperature will increase again. It changes into vapor if the heat is enough.
40 g ice at - 20°C -» 40 g ice at 0°C -» 40 g water at 0°C -» 40 g water at t°C
q 3 = m x с x At = (40 g) x (0.5 cal/ g °C) x (20°C) = 400 ca^
ah
q 2 = m x Lf = (40 g) x (80 cal/g) = 3200 cal J qtotal = 4 i + q 2 = 400 + 3200 = 3600 cal

^difference = 4000 - 3600 = 400 cal. It will be used to warm water.

q 3 = m x с x At => 400 cal = (40 g) x (1 cal/g°C) x (t°C) => t = 10°C

EXER C ISE 5.4 If 6600 calorics arc given to 20 g of ice at - 30°C, what will be the final physical state
and the temperature? a t l 0 0 ° C 5 g v a p o r - 1 5 g wat e r

EXAM PLE 5.7 U sin g H e a t R e la tio n s h ip s in P h a se C hanges

Problem / 2 0 g o f water vapor at U 0°C are sent onto 100 grams of ice at - 20°C. Find the final physical
state and the temperature.
Solution : When the vapor and ice are mixed, some heat will be transferred from the vapor to the icc. And the
amount o f heal given is always equal to the amount of heat taken. To solve this kind o f problem we will follow
the method used below.
1. Calculate the heat given by vapor until it becomes liquid water at 0 °C.
Vapor at 110 °C —> vapor at 100 °C -» water at 100 °C -> water at 0 °C
q, = m x с x At = (20 g) x (0.5 cal/g °C) x (10 °C) - 100 cal
q2 - in x L v = (20 g) x (540 cal/g) = 10800 cal [• qiost - + q2 + q3 - 12900 cal
q3 = m x с x At = (20 g) x (1 cal/g °C) x (100 °C) = 2000 cal J
2. Calculate the heat gained by ice until it becomes liquid water at 0 °C.
Ice at - 20°C -» icc at 0°C-> water at 0°C
q 3 = m x с x At = (100 g) x (0.5 cal/g°C) x (20°C) = 1000 cal r
q2 = m x Lf = (100 g) x (80 cal/g) = 8000 cal ■'^gained 9000 cal
3. Calculate the difference between heat lost and heat gained
^difference = «fo* ‘ 4ga,ned - 12900 cat - 9000 cal = 3900 cal
148 Chapter 5

4. Since qlosl > q ained, then, q d iffe re n c e will be used to increase the temperature o f water from 0°C to any tem­
perature.
^difference = m total x c x At => 3900 cal = 120 g x 1 cal/g °C X (tf - 0) => tf = 32.5 °C

EXER C ISE 5.5 5 g o f water vapor at 150°C are sent onto 50 g o f ice at - 20°C. Find the final physical
state and the temperature. a t o ° C 4 0 . 3 g w a t e r - 1 4 . 7 g ice

5.2 VAPOR PRESSURE AND

BOILING POINT
T h e m o lecu les o f a liquid escap e from the su rface o f a liquid
by evap o ratio n . S o m e l i q u i d s , s u c h a s e t h e r , a l c o h o l , e v a p o r a t e
q u i t e r a p i d l y . T h e s e l i q u i d s a r e c a l l e d volatile l i q u i d s . E v a p o ra ­

ill tio n m ay be ex p lain e d in te rm s o f k in e tic m o le c u la r th e o ry o f

m atter. Ju st as in a gas, at any tem p eratu re the m o le cu le s o f a
liq u id do n o t m o v e at the sam e speed, som e rapidly, m any at in­
te rm e d ia te speed s, and so m e v e ry slo w ly . A ra p id ly m o v in g
m o lec u le n e ar the surface o f th e liquid m ay p o sse ss e n o u g h k i­
n etic en ergy to ov erco m e the attractio n o f its n e ig h b o rin g m o le­
cules and escape from the liquid. A s the tem perature increases the
fraction o f energetic m olecules increases, consequently the rate o f
ev a p o ra tio n increases. I f a liq u id in a clo sed c o n ta in e r e v a p o ­
FIGURE 5.5 d y n a m ic e q u ilib riu m
e x is ts b e tw e e n a liquid a n d its va p o r in rates, the v ap o r m olecules can n o t escape from the v icinity o f the
a c lo s e d co n ta in e r a t a certain te m p e ra ­ liq uid. In the co u rse o f th e ir random m o tio n , so m e o f th e v ap o r
ture. In equilibrium th e rate o f e v a p o ra ­ m o lecu les return to the liquid. T h e pro cess fo r w ater can be re p ­
tion a n d rate o f c o n d e n sa tio n are equal. resented by using a double arrow.

H 20 (1) H2 0 (g)
A s e v a p o ra tio n p ro ce ed s th e n u m b e r o f m o le c u le s in
th e v a p o r state in creases, and in tu rn the rate o f co n d e n sa ­
tio n increases. W h en if the rate o f ev ap o ratio n and the rate
o f cond en satio n are equal, the co n d itio n is called a state o f
dy n am ic equilibrium. S ee F ig u re 5.5. T h e eq u ilib riu m is
d y n am ic b ec au se th e re are tw o o p p o sin g ch a n g es tak in g
place at the sam e rate, b u t no changes in th e am ounts o f in
liquid and vapor. T he concentration o f the m o lecules in the
v ap o r is co n stan t at eq u ilib riu m . T h e p ressu re th a t the v a ­
p o r exerts is also constant. T h e pressu re o f v a p o r in e q u ili­
brium w ith its liq u id at a giv en te m p era tu re is c alled the
T em p e ratu re (°C)
vapor pressure o f th e liq u id . T h e v a p o r p re ssu re o f a
given liquid is determ ined by the tem perature and increases
T h e equilibrium v a p o r p r e s s u r e s , _
,, : , , , w hen the tem p eratu re is raised. S ee F ig u re 5.6.
o f fo u r c o m m o n s u b s ta n c e s a s a fu n ctio n o f 1 b
te m p e ra tu re . T h e in te rse c tio n o f a c u rv e with T h e v a p o r p re ssu re s o f w ate r, e th y l alco h o l, and die-
th e d a s h e d line a t 7 6 0 torr in d ic a te s th e n o rm a l th y l e th e r a t 2 0 °C are re s p e c tiv e ly 2 3 .8 m m H g , 4 4.1
boiling p o in t o f th a t s u b s ta n c e . W h en th e e x te r- m m H g and 4 4 2 m m H g . A t 4 0 °C , th e v a p o r p re ssu re o f
n a l p r e s s u r e o v e r th e liquid in c r e a se s th e boiling
tem p e ra tu re o f th e liquid in c r e a se s
 Condensed Phases o f M atter Liquids and Solids 149

water is 55.3 m m H g, o f ethyl alcohol is 135 m m H g. D ieth yl ether b oils at

34.6 °C. The vapor pressure o f every liquid increases as the temperature is
raised. A list o f the vapor pressures o f water at various temperatures is given
in Table 3.1 .
B oilin g Poin t
The temperature at which the vapor pressure o f a liquid becom es equal to
the external pressure is called the boiling point. The temperature o f a b o il­
ing liquid remains constant until all the liquid has been vaporized.
The boiling point o f a liquid changes with changes in external pressure.
W ater, for exam ple, w ill b oil at 9 8 .6 °C at a pressure o f 0 .9 5 0 atm and at
101.4 °C at a pressure o f 1.05 atm. The normal boiling point o f a liquid is
the temperature at w hich the vapor pressure o f that liquid is exactly one stan­
dard atm osphere, 76 0 m m H g. A s the atm ospheric pressure rises, the boiling
point rises, and the boiling temperature falls if the atm ospheric pressure falls.
See Table 5.2 for the boiling temperature o f som e substances.

E X A M P L E 5.8 U n d ersta n d ing B oiling Point - V apor P ressure Relation

Problem : Use the graph given in Figure 5.6 to answer these questions, (a) At what temperature will the
ether boil if the pressure over the liquid is 1) 400 mmHg 2) 600 mmHg 3) 800 mmHg. (b) W here will you
cook your food in boiling water faster, at sea level or at the top of Ararat Mountain where the pressure is about
500 mmHg ?
Solution : a) A liquid boils when its vapor pressure becomes equal to the pressure over the liquid. The graph
indicates that the vapor pressure o f ether is 400 mmHg at about 17°C, 600 mmHg at about 30°C, and 800
mmHg at about 35°C. Then, ether will boil at 17°C, 30°C, and 35°C under the indicated pressures respectively,
(b) Under 500 torr the water will boil about 90°C. At sea level it boils at 100°C. At the top of Ararat Mountain,
food in boiling water cooks more slowly than at sea level. Cooking process is directly proportional to the tem ­
perature.

EXERCISE 5.6 The following vapor pressure data arc available for liquid metallic zinc.
P(mmHg) 10 40 100 400
t(°C) 593 673 736 844
From an appropriate plot of the data, determine the normal boiling point.

E X A M P L E 5.9 C om p a rin g the B oiling Points, U sin g V ap or P ressure o f L iqu ids

Problem : The vapor pressures o f the liquids A, В and С are 40 mmHg, 60 mmHg, and 100mmHgat the
same temperature respectively. List them in order o f increasing boiling points.
Solution : Boiling point is the temperature at which the vapor pressure on its liquid is exactly equal to the
outer pressure. In our example, the boiling point o f the A is the highest. Because its vapor pressure is the lowest
among them. To get its vapor pressure equal to outer pressure we must heat it to a higher temperature. The boil­
ing point o f С is the lowest. In that case, the order is С, B, A.

EXER C ISE 5.7 The heat of vaporization of H20 is about 1.5 times that o f CC14. Which liquid should
have larger surface tension ?
150 Chapter 5

5.3 SOLUTIONS
A so lu tio n can be defined as a ho m o g en eo u s m ix tu re o f to o r m o re su b ­
sta n c e s. T h e re are to c o m p o n e n ts o f a so lu tio n so lu te and so lv e n t* . T h e
co m p o n en t in sm a ller p ro p o rtio n is ca lle d solute, and the co m p o n en t in larger
a m o u n t is c a lle d solvent. F o r exam ple, w hen salt is stirred w ith en o u g h w ater,
th e salt d isso lv es in w ater. T h e m o lecu les (actu a lly io n s) o f salt b eco m e u n i­
fo rm ly d istrib u te d th ro u g h o u t the w ater. So the salty w a te r is a h o m o g e o u s
m ix tu re o f salt and w ater. H ere salt is solute, w a ter is solvent, and salty w a ter
is solution.
S o lu tio n s m ay be g aseous (such as air, o r any gas m ix tu re), solid (such
as alloys o f m etals), or liquid (such as salty w ater). See T ab le 5.2 and 5.3.
TA BLE 5.2 Some Alloys TABLE 5.3 Solutions
r \ r
N am e C o m p o sitio n o f A lloy K inds C o m m o n E x am p les
(P e rce n t by m ass) G as in liquid A m m o n ia in w ater o r C 0 2 in w ater
L iquid in a liquid G a so lin e o r v in e g a r (a ce tic acid in w ater)
S ta in le ss steel 76 Fe, 16 Cr, 8 Ni S olid in a liquid S alt in w ater
A ln ic o 61 Fe, 17 N i. 12 C o ,1 0 Al G as in a gas A ir
N ic h ro m e 60 Ni, 25 Fe, 15 C r L iquid in a gas W a te r v a p o r in air
B ra ss 60 9 0 C u, 4 0 -1 0 Z n S o lid in a gas Io d in e v a p o r in air
B ro n z e 80 Cu, 15 Sn, 5 Zn G as in a solid A llo y o f p a lla d iu m and hy d ro g en
G o ld ( 16 k a rat ) 67 Au, 33 Cu L iquid in a solid B e n ze n e in ru b b e r o r m erc u ry in silv er
S o ft so ld e r 50 Sn, 50 Pb S olid in a solid C a rb o n in iron (ste el)
J

In ch em istry w e u su ally deal w ith liquid so lu tio n s, esp ec ially a q u e o u s

so lu tio n s (so lu tio n s in w h ich w a te r is so lv en t). A n aqueos so lu tio n (o r any
solution) m ay contain m ore than one kind o f solute. F o r exam ple seaw ater is a
solution co n tain ing o v er 60 kinds o f differen t solutes.
Solutions m ay be classified according to the relative am ounts o f solute to
s o lv e n t (w h ich is u su a lly c a lle d c o n c e n tr a tio n o f th e solu tio n ). A so lu tio n
w ith a sm all p ro p o rtio n o f solute to so lv en t is said to b e d ilu te, and one w ith
a larg e p ro p o rtio n o f solute to so lv en t is said to be co n ce n tr a ted . A so lu tio n
is sa tu ra ted w h en no m o re so lu te can be d isso lv e d in the so lu tio n a t a given
tem perature. In a saturated solution a dynam ic equilibrium exists betw een the
d isso lv e d so lu te and u n d isso lv c d solute. In su ch a so lu tio n , th e rate o f d is­
solv in g and the rate o f precipitation arc equal, so th at the am ount o f solute d is­
solved in the solution rem ains constant. This constant concentration o f a solute
in its sa tu ra te d so lu tio n is refe rred to the solu b ility o f the solute. I f a solution
is cap ab le o f d isso lv in g som e m ore solute, it is called u n sa tu r a te d solution.
A n u n satu ratcd so lu tio n co n tain s Jless so lu te d isso lv e d in a g iv en q u an tity o f
so lv e n t than d o es a saturated so lu tio n o f the sam e so lu te in the sam e qu an tity
o f so lv en t at the sam e tem perature. If a saturated solution o f a solid is prepared
at a h ig h tem p eratu re, and th en the so lu tio n is co o led , n o rm a lly so m e o f the
so lu te c ry sta lliz e s o u t o f the solution. In som e cases this c ry sta lliz atio n m ay
n o t o ccur.In this case the cool solution contains m ore solute than it w ould n o r­
m ally co n tain at a g iv en tem perature. S uch a so lu tio n is called su p e rsa tu r a t­
ed solution. S u persaturated solutions are unstable. A gitation o r the ad d ition o f
When the amounts of components are equal the choice o f solute and solvent is arbitrary
 Condensed, Phases o f M atter Liquids and Solids 151

a few solu te crystals m ay start the cry stallization o f the e x cess solute, produc-
ing a saturated solution.
760 mmHg /
Vapor pressure

ж 1/ \
\
5.3.1 P R O P E R T IE S OF S O L U T IO N S
>
\ ^

b.p (solution)
W h en a n o n v o la tile so lu te is add ed to a so lv en t, it d isso lv es and p ro ­
i>.p (liquid)
\

duces a hom ogeneous m ixture. As a result a fraction o f the surface o f the so lu ­

1
\

tion is occu pied by th e solute m o lecules (o r ions). Since the v a p o r pressu re o f

Temperature a so lv en t is determ ined by the frequency o f escap e o f m o lecu les from its su r­
face, the probability o f escaping m o lecules o f so lv en t from a u n it area o f solu-
FIGURE 5 7 T h e a d d i- tio n wil1 be less th a n ^г о т the sam e area Pu re so lv e n t- C o n se q u en tly , the
tion o f s o lu te p a r tic le s v a p o r p ressu re o f a so lu tio n is lo w e r th an its p u re so lv en t at a g iv en tem p era-
lo w ers th e va p o r p r e s s u r e ture. T h e d ecrease in the v ap o r pressure d ep ends on the fraction o f the surface
o f th e s o lv e n t, th e re fo re , occu p ied by the solute particles, o r the co n cen tratio n o f solute in the solution,
in c r e a se s th e boiling p o in t not o n m ass o r sjze 0 f the solute particles b u t th eir num ber.
o f solution.

E X A M P L E 5 .1 0 C o m p a r in g V a p o r P r e ssu r e s o f S o lu tio n s a n d P u r e L iq u id s
Problem: Three containers have pure water, NaCl solution and pure alcohol respectively. List them in order
of increasing vapor pressures at the same temperature.
Solution: Vapor pressure of pure liquids is higher than their solutions. Because the boiling point o f the so­
lution of a liquid with a solid is higher than the liquid. In that case the vapor pressure of pure water is higher
than NaCl solution at the same temperature. The boiling point of pure alcohol is lower than pure water. Then,
the vapor pressure of pure ilcohol is higher than pure water. A substance which has a lower boiling point has a
higher vapor pressure. The increasing order is NaCl solution, pure water, pure alcohol.

W e k n o w th a t a liq u id b o ils w hen its v a p o r p re ssu re b ec o m e s eq u al to

th e p rev ailin g atm ospheric pressure. S ince a so lu tio n has a lo w e r v a p o r p re s­
sure th an its solvent, th en a h ig h e r te m p eratu re is n eed ed to p u t e n o u g h so l­
v en t p articles into the vap o r phase to reach the atm ospheric pressure. T h e b o il­
юс -
in g p o in t o f a so lu tio n is, therefore, h ig h e r th an th a t o f the p u re solvent. T h is
is called the elevation o f boiling p o in t. See F igure 5.7, and 5.8.
H ow does the addition o f a nonvolatile solute affect the freezing p o in t o f
a solution ? W hen the tem perature o f a solution is decreased the kinetic energy
t im e o f th e m o lecules (o r th e structural units) o f the liq u id decreases. A s th e speed
o f the particles d ecreases the attractive forces betw een particles beco m e m ore
FIGURE 5.8 A so lu tio n effectiv e and the p articles rem ain to g eth er in a certain g eo m etry and the c ry s­
b e g in s to boil at a hig h er
tals o f th e so lv en t are form ed (freezing). T h e ex isten ce o f the solute particles
tem p e ra tu re tha n its p u re
s o lv e n t
m ak es d iffic u lt the p ro b ab ility o f so lv en t p articles to b eco m e together. S o lu ­
tio n s, th en , freezes at a lo w e r tem p e ratu re th a n th e pure so lv e n t alone. B e ­
cau se o f the d ep ressio n in the freezin g p oint, th e se aw a ter d o es n o t freeze as
readily as fresh w ater lakes and rivers do. S ee F ig.5.9.
T h e p h enom enon o f freezing p o int d e p ressio n has practical applications.
T h e b e s t k n o w n ap p licatio n s are m eth o d s used to lo w e r the freezin g p o in t o f
w ater. A n antifreeze (usually ethylene glycol), w hen added to the cooling sys-
152 Chapter 5

tem o f an autom obile, protects coolant from freezing in cold weather. N aC l, or

°c p u re w ater СаС 1г are frequently used to m elt ice on roads in winter.

\\T It has been found experim entally that 1 m o l o f a n o nvolatile a n d nonion­

0 ............ 4.
izin g so lu te p a r tic le s w ill ra ise the b o ilin g te m p era tu re o f 1 0 0 0 g o f w a te r
0 .5 1 °C a n d w ill low er the fr e e z in g p o in t o f 1000 g o f w a te r 1.8 6 °C . For ex ­
r e ­ ample i f 180 g sugar (lm o l) is dissolved in 1000 g H20 the solution w ill begin
s o lu tio n
to boil at 100.51°C , and begin to freeze at -1.86°C . If 58.5 g N aC l (1 m ol) is
d isso lv ed in water the solution begins to b oil at 101.02°C , and begins to
tim e
freeze at -3.72°C because 1 m ol NaCl produces tw o m oles o f particles in w a­
FIGURE 5.9 A solution ter ( lm o l N a +, and 1 m ol Cl'). The solution prepared by d isso lv in g 1 m ol
always freezes at a lower
CaCl 2 in 1000 g o f water freezes approximately 3 x l.8 6 °C below 0°C and boils
temperature than its pure
solvent 3x0.51°C above 100°C.

E X A M P L E 5.11 F r e e z in g P o in t D e p r e s s io n a n d B o ilin g P o in t E le v a tio n .

Problem : How much does the boiling and freezing point of water change when 54 g glucose, C ^H ^O g,
(a nonionizing solid) is dissolved in 250 g o f water ? СбН 120 б = 180 g/mol.
Solution : The boiling point elevation of a solution is directly proportional to the number o f moles of parti­
cles dissolved in 1000 g of water. Therefore, let us find the mole number o f glucose dissolved in 1000 g of wa­
ter. n = m/MW = 54 g/180 g/mol = 0.3 mol (in 250 g o f water)
If 250 g water contains 0.3 mol solute
,2 mol o f solute
1000 g water contains x
Since the solute is nonionizing, then, the total number of moles of solute is 1.2 mol.
If 1 mol particle increases the boiling point o f 1000 g of water by 0.51°C
1.2 mol particle increases the boiling point of 1000 g of water______ x } x = 0.61°C

So the solution will boil at 100.61°C.

As to the freezing point depression:
1 mol particle in 1000 g water lowers the freezing point
1.2 mol particle in 1000 g water lowers the freezing point
1.86°C
x
J x = 2.23°C

The solution will begin to freeze at approximately -2.23°C.

EX E R C ISE 5.8 Calculate the boiling and freezing point of the solution made by dissolving 51.3 g of
C t 2 H 22O n in 200 g of water. C ) 2H 220 ] i = 342 g/mol 100.38°C, - l . 4 ° C

EXAMPLE 5 .1 2 F r e e z in g P o in t D e p r e ssio n
Problem : N aCl is an ionic solid. It produces N a+ and СГ ions in water. W hen 11.7 g o f NaCl are dis­
solved in 250 g o f water, what is the freezing point of the solution ?
Solution : In 250 g of water , 11.7 g of NaCl are dissolved.
The amount o f NaCl dissolved in 1000 g of water is 1 1.7 x 4 = 46.8 g
NaCl (s) -» Na+ (aq) + Cl '(a q )
n N a C i- —- = 0.8 m ol lm ol lmol lmol
5 ‘ g 0.8 mol x i = 0.8 mol x 2 = 0.8 mol
 Condensed Phases o f M atter Liquids and Solids 153

The total number of moles o f species in the solution is 0,8 + 0.8 = 1.6 mol

x *
Then, the depression in the freezing point o f the solution is - 2.98°C

EX E R C IS E 5 , £ h ow many gram s of C aC l 2 must be dissolved in 500 g of water to raise the boiling

point to 103 .0 6 °C ? ' v 111 g

E X A M P L E 5.13 C a lc u la tin g M o le c u la r W e ig h t F ro m F r e e z in g P o in t D e p r e ssio n

Problem .'T h e addition o f l 5 g of nonionizing compound reduces the freezing point of 500 g o f water from
0°C to -0.93°C. W hat is the molecular weight of the compound ?
Solution:First, we calculate the gram s o f substance dissolved in 1000 g of water. In 500 g of water 15 g
substance is dissolved. In 1000 g of water 30 g of solute will be dissolved. .Second, we calculate the mole num ­
ber of solute that lowers the freezing point of 1000 g of water by 0.93°C.
I l l inol Mihstjiicc in 10(H) t 1l; () lowers the liee/ing point by 1.86°C .
jc mol 0.93 j X = 0-5 mo1 ° f substance
Then the mass o f 0.5 mol compound is 30 g.

n = -DL. => m w = — = 3 0 £ = 60 g/mol

iMW n 0.5 mol

EXER C ISE 5.10 When 13.8 g of nonionizing compound arc dissolved in 100 g of water, the boiling
point of the water becomes 100.765°C. Calculate the molecular weight of the compound. 92 g / mo l

EXERCISE 5.11 When 24 g of a nonionizing solute are dissolved in 250 g of water, the freezing point
is lowered to - 5.58°C. Calculate the molecular weight of the solute. 32g

E X E R C ISE 5.12 How many grams of glycerine, C 3H 5(OH) 3 must be dissolved in 400 g of water to
lower the freezing point to -27.9°C ? C 3H 5 (OH ) 3 = 92 g/mol ’ 552 g

5 .3 .2 C O N C E N T R A T IO N S OF S O L U T IO N S
C oncen tration is a general term to express ho w m uch solute is dissolved
in a given q u an tity o f so lv en t (or solution). T h ere are m any w ays to describe
the concen tration o f a solution. T he com m on term s used to express co n c en tra­
tions o f solutions are : (1) P ercent C oncentration b y m ass (2) M o la r C oncen­
tration (3) N orm al C oncentration (4) M olal C oncentration (5) M ole Fraction.
H ere w e w ill exam ine p ercen t co m position by m ass, m o la r co n cen tratio n and
norm al concentration
5.3.2.1 PERCENTAGE CONCENTRATION
The g ra m s o f so lute d isso lved in 100 g o f so lu tio n is ca lled the p e r c e n t­
a g e c o n c e n tr a tio n o f the so lution. T h e p ercen tag e o f so lute in th e so lu tio n
154 Chapter 5

m ay be g iv en b y the expression :

C o n c en tra tio n = m s,,luU! x 100

Ot solution

For example, a 20 % aqueous solution o f potassium nitrate contains 20 g of

KNO 3 and 80 g of H 2O.
W hen both solute and solvent are liquids, the concentration is stated as per­
cents by volum e.___________________________________________________
C o n ce n tr a tio n b y v o lu m e = - Y ° l u i n c (>f s(>lu te x 100
______________________________ V o lu m e o f s o lu t io n _______

E X A M P L E 5.14 C a lc u la tin g P e r c e n ta g e C o n c e n tr a tio n

Problem : A salt-water solution is prepared by dissolving 20 g NaCl in 230 g of water. W hat is the percent
by mass o f salt in the solution ?
Solution : The percentage concentration o f a solution is the mass in grams of solute dissolved in 100 g o f so­
lution. In our example 20 g solute and 230 g solvent produce 250 g of solution. In other words, 250 g of solu­
tion contains 20 g o f solute. Then the mass o f solute in 100 g solution is :
If 250 g solution contains 20 g solute
j x = 8 g or 8 %
100 g solution x
Or you may solve the problem by using the formula : % Concentration = т *>|ии: x 100
^ solution
C = — —— x 100 = 8
20 + 230

EXERCISE 5.13 Calculate the percentage by mass of solute in each of the following solutions.
a) A solution prepared by dissolving 20 g sugar in 60 g of water, b) A solution prepared by dissolving 20 mL of
ethyl alcohol (d=0.8 g/mL) in enough water to produce 250 mL of a solution with density of 0.98 g/mL.
a)25% b)6.53%

E X A M P LE 5 .15 Understanding Percentage Concentration

Problem : Suppose that you have a 160 g of solution that is 20 % sugar by mass. Calculate the percentage
concentration of the new solution resulting after
a) it is mixed with 40 g o f water. b) 32 g of water is evaporated from the original solution,
c) it is mixed with 40 g of sugar. d) it is mixed with 40 g water and 40 g o f sugar.
e) it is mixed with 840 g o f solution containing 5 % sugar.
Solution : a) 160 g of 20 % sugar solution contains 160x20/100 = 32 g of sugar. The addition 40 g of water
increases the mass of the solution to (160+40) or 200 g. Now 200 g solution contains 32 g sugar. Then, the per­
centage of sugar in the solution i s :

% C = - ^ ^ x 100 =* % C = — x 100 = 16=* 16 %

^ solution 200

b) When water is evaporated, just the mass of solution (or solvent) decreases.

m sugar = 32 g 1 % с = -YL x 100 = 25 => 25 %

m soluiion = 1 6 0 - 3 2 = 128 g J 128
 Condensed Phases o f M atter Liquids and Solids 155

c) The addition o f sugar (or solute) increases both mass o f solute and mass of solution.
msugar = 32 + 40 = 72 g
I % C = — X 100 = 36 36%
tn solution — 160 + 40 —200 g J 200

d) The addition o f water and sugar to the solution increases both the mass o f solute and mass of solution.
^ solute = 32 + 40 = 72 g 1 m„ 72
, c = — X 100 = 30: 30 %
*f*solution = 160 + 40 + 40 = 240 g 240
e) W hen two different solutions of the same solute are mixed, the mass o f solute in the resulting solution is the
sum of the solutes in the solutions mixed.
5 ; 74 g
m «лае = m i + m 2 = 32 + 840 x

nt solution = 160 + 840 = 1000 g

100
} 74
1000
x 100 = 7.4 =* 7.4

EXER C ISE 5.14 Calculate each of the following.

a) grams o f NaOH in 800 g solution that is 20 % NaOH by mass, b) the percentage concentration o f the solution
resulted by mixing 150 g solution that is 20 % sugar by mass, 50 g of solution that is 30 % sugar by mass, 85
g Water, and 15 g of sugar, c) the grams of NaCl that must be added to' 150 g of 10 % NaCl solution so that the
percentage o f NaCl in the resulting solution is 20 % .^> lh e masses of 20 % and 40 % sugar solutions that must
be’mixed to obtain 400 g of solution containing 25 % sugar by mass.
a )1 6 0 b )20 % c)18.7S g d )3 0 0 g and 100 g

E X A M P L E 5.16 Understanding Percentage Concentration

Problem : Concentrated nitric acid solution has density of 1.42 g/mL and contains 72 % HNO 3 by mass.
How many grams of HNO 3 are there in 500 mL of this concentrated solution ?
Solution : The problem may b e solved by the following steps.
500 mL solution Д ? g solution Д ? g HNO 3
Step I : W e know the density and volume o f the solution so the mass of 500 mL solution is :
m = d x V = 1.42 g/mL x 500 mL = 710 g
Step I I : The solution contains 72 % HNO 3 by mass ( l i g HNO 3/IOO g solution)
Then, 710 g solution will contain :
72 g HNO 3
710 g solution x = 511.2 g HNO3
,100 g solution

EXER C ISE 5.15 A student needs 109.5 g o f HCI for a reaction. W hat volume of concentrated hydro­
chloric acid solution with a density of 1.2 g/mL and containing 36.5 % HCI by mass contains 109.5 g o f HCI ?
HC1=36.5 2 5 0 mL

EXECISE 5.16 10 mol o f H 2S 0 4 are used to prepare 1000 mL o f 49 % H2S 0 4 solution by mass. W hat
156 Chapter 5

5.3.2.2 MOLAR CONCENTRATION (MOLARITY)

The n u m b e r o f m o les o f so lu te d isso lv e d in 1 liter o f so lu tio n is ca lle d
the m o la r c o n c e n tr a tio n or m o la r ity (ab b rev iated M ) o f the so lu tio n . M o ­
larity m ay be calculated by d iv id in g the m oles o f solute by the v o lu m e o f the
solution in liters.
. .. m oles o f solute ^
m o l a r i t y = ------------------------- —
volume o f solution

O ne o f the ad v an tag es o f ex p ressin g the c o n c en tratio n o f a so lu tio n is

th a t it e n a b le s us to se le ct a desired n u m b e r o f m o les o f so lu te sim ply by
m e a su rin g o u t the app ro p riate v o lu m e o f solution. F o r ex am p le a 2 M N aC l
solution co n tains 2 m ol o f N aC l in 1 lite r o f solution. I f 0.5 m ol N aC l is n ee d ­
ed w h at o n e sh ould do is simply to m ea su re o u t 25 0 m L o f 2 M N aC l so lu ­
tion.

E X A M P L E 5 .17 P r e p a r i n g a S o lu tio n W i t h K n o w n M o la r C o n c e n tr a tio n

Problem : Describe how to prepare 1 L of 1 M NaOH solution. NaOH = 40 g/mol.
Solution :
Step I : Calculate the number o f moles and the mass of NaOH necessary.

M = — = > n = M x V = l mol/L x 1 L = 1 mol, m = n x MW = 1 mol x — - = 40 g NaOH

V 1 mol

Step II :Weigh out 40 g o f NaOH, and place it into a volumetric flask with a 1 L mark on it.
Step III : Add about 300 mL (or any volume of water less than 1000 mL) o f pure water into the volumetric
flask and shake it well until all the NaOH dissolves. If some NaOH remains undissolvcd add some more water
and dissolve the NaOH.
Step IV : Add just enough water to the solution to make up its volume exactly 1 L (until the volume of the
solution reaches the calibration mark). The operation is shown in Fiettrc 5.10

O n e m o le o f th e s o lu te ( i t s fo rm u la Th e f ' f 18 P |aced. W a te r is a d d e d ' 3 " d T 'm l k T t h e

w e ig h t in g r a m s ) is c a re fu lly w e ig h e d . m a H lte r ^ m e t r i c th e s o lu te is b ro u g h t v o lu m e n f th e
fla s k . in to s o lu tio n . , " , ,
s o lu tio n 1 lite r

FIGURE 5.10P ro c e d u re o f p rep a ra tio n o f 1 L o f a 1 M N a O H solution, (a) W eig h o u t 1 m o l o f N a O H (40 g ) (b)

A d d th e N aO H to a 1 L vo lu m etric fla sk (c) A d d w a ter to d is so lv e th e N aOH , th e n m o re w a ter until th e v o lu m e o f
th e solution is e x a c tly 1 L.
 Condensed Phases o f Matter Liquids and Solids 157

EXERCISE 5.17 Describe how 10 prepare 500 ml. ol' 1.5 M Na>5(.).i solution. ,\.nNO_t - 142 g/mol

E X A M P L E 5.18 C a lc u la tio n s B ased on M o la r C o n c e n tr a tio n

Problem : 30 g NaOH is dissolved in enough wafer to form 600 mL of solution. W hat is the molarity of the
solution ?
Solution : 30 g NaOH -> ? mol NaOH -> ? M NaOH
n Na0H = 30 & = 0.75 mol M = —= _ j 25 mo)/L = L25 M
40 g/mol V 0.6 L

E X A M P L E 5 . 1 9 C a lc u la tio n s B a se d on M o la r C o n c e n tr a tio n
Problem : l I .2 liters of NH 3 gas measured at STP is dissolved in water to prepare 5 liters o f solution. Calcu­
late the molarity of the solution.
Solution : 11.2 L NH 3 —> ? mol NH 3 -4 ? M NH 3
n N1, = 11 2 1' = 0.5 mol M =—= = 0.1 M
1 22.4 L/m ol V 5L

EXERCISE 5.18 C alculate the m olarity oh each ol the follow ing solutions.
a) 5 L solution containing 2 mol B a d ? h) 250 mL. solution containing 7 g ol KOI I (56 g/m ol) c) 500 m L o f
solution containing 6.02 x 1 0 " N II 3 m olecules d) 500 m l. solution containing 28.75 mL. C 2 H«;OH (46 g/m ol
and d = 0.8 g/mL.) e.t 600 ml., solution containing 6.72 L HCI at STP (.36.5 g/m ol) 0 I 250 mL o f solution c o n ­
taining 42.5 g o f NaNO.i (85 g/m ol) sam ple that is 80 pure, g) Л solution, with a density o f 1.17 g/m L, p re­
pared by disso lv in g 6 8 g KOI (74.5 g/m ol) in 200 g of w ater. a ) 0 . 4 Ы0. 5 c)0.2 d ) l e)0.5 f ) 0. 3 2 g ) 4

E X A M P L E 5 .20 Calculating Quantity of Solute

Problem : How- many grams of Ре(Ь'Оз )2 arc required to make 400 mL o f 0.5 M Fc(NC>3)2 Fe(N 03)2 = 180
Solution : (400 mL, 0.5 M) F c(N 0 3)2 -» ? mol F e(N 0 3)2 -> ? g F c (N 0 3)2

M = JL or n = M x V = 0.5 mol/L x 0.4 L = 0.2 mol Fc(NO0 2 m = n x MW=> 111 = 0.2 x 180 = 36 g F e (N 0 ^ 2

EXERCISE 5.19 CqW ulate the quantity o f solutes in gram s necessary to prepare each o f the follow ing
solutions, a) 2 liters of IM H N O , (M W = 63 g/m ol) h) 500 m L o f 1.5 M CaBig (M W = 2 0 0 g /m o l)c ) 250 mL
o f 2 M C H 3OH solution from pure C H 3OH that has a d cn sit\ o f 0.8 g/ml... (C H 3 OH = 32 'g/mol)
ti)l2(>K b)l50g c)1nr 20ml.
EX A M P LE 5.21 C a lc u la tio n s B a sed on M o la r C o n c e n tr a tio n
Problem : How many liters of 3 M NaOH solution can be prepared with 360 g NaOH ?
Solution : 360 g NaOH -> ? mol NaOH -> ? L solution У

n Na01l = 360 g = 9 mol M = — => V = 9 mo1 = 3 liters solution

________________ 40 g/mol_____________________ V_________ 3 mol/L________________________________

E X A M P L E 5.22 C a lc u la tin g M o la r ity F ron t D e n sity an d P e r c e n ta g e C o n c e n tr a tio n

Problem : All aqueous solution of methyl alcohol CH 3OH is 16 % CH 3OH by mass and has a density of
0.9 g/mL. Calculate the molarity of ihe solution. CH 3OH = 32 g/mol.
158 Chapter 5

Solution : Molarity is the number of moles of solute in 1000 mL o f solution. To find the molarity of the
solution, what w e should do is to calculate the number of moles ®f solute in 1000 mL o f solution. Therefore let
us assume the volume of the solution to be 1000 mL or 1 L. The solution oftfie problem now includes the fol­
lowing steps.
1000 mL solution 4 ? g solution 4 1? g CH3O H 4 1? mol CH3OH 4 ? M CH3O H

Step I : Mass of 1000 mL solution : m = V x d = 1000 mL x 0.9 g/mL = 900 g

Step II : Mass of C H 3OH in 900 g solution :
The solution is 16 % C H 3OH by mass. Then 16 % of 900 gives the mass of CH3OH in the solution or

m CH,oH= 900 g solution x = 144 g of С Ь ф Н

100 g solution
Step III :пСНз0Н = m/MW = 144 g/32 g/mol = 4.5 mol.
Step IV :Since 4.5 mol of CH3OH are present in 1 L of solution, then, the molarity is :
m = n/V - 4.5 mol/L = 4.5 M
All these steps may be united in a formula.

1000 mL solution x d g/mL x —C .S so^ul:e— л

M = ____________________________100 g solution ^ 10 x d x С
M =
MW of solute x I L MW

In this formula, d is density in g/mL, С is the percentage of solute by mass in the solution, and MW is the m o­
lecular weight of the solute.
Using this formula we can find the molarity of the solution easily.
d = 0.9 g / m L , С =16, MW = 32 g/mol => M _ 1° x 0.9 x 16 _ 4 ^ M

— i ----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
EX E R C IS E 5.20 Concentrated MCI solution is 36.5 % MCIbymass and has adensity o f 1.2 g/mL..
What is the molarity of the solution ? MCI = 36.5 g/mol 12 M

E X A M P L E 5.23 Calculation of Atomic Weight From Molar Concentration.

Problem .'3.1 g MgX 2 is used to prepare 500 mL of 0.1 M MgX 2 solution. W hat is the atomic weight of
X? M g = 24 g/mol
Solution : The steps involved in the solution of the problem are :
(500 mL, 0.1 M) MgX 2 ? mol MgX 2 -> MW of MgX 2 -> AW o f X

Umex = m x V = 0.1 mol/L x 0.5 L = 0.05 mol and M W Nb.x = m/n = 3,1 ^— = 62 g/mol
^ 2 '^ 2 0.05 mol
The atomic weight o f X is :
MgX 2 = 62 => 24 + 2X = 62 => X = 19 g/mol

EXERCISE 5.21 19 .36 g of X (N 0 3)3 i.s used in the preparation of 400 mL of 0.2 M solution. Calculate ,
the atomic weight of X. N = 14, О = 16 56 g/mol
 Condensed Phases o f Mattel' Liquids and Solids 159

5 .3 .3 DILUTION
W e o ften p rep are a less concentrated so lu tio n from a m o re con cen trated
so lu tio n sim p ly by ad ding w a ter (o r so lv en t) to th e m o re c o n ce n trated so lu ­
tion. T h is is called dilution. W h en w e d ilu te a so lu tio n by a d d in g m ore so l­
vent, th e n u m b er o f m oles o f solute does n o t change. O r
fo o tin e in concentrated solution ~ ^ so lu te in diluted solution

since M = n/V or n = M xV

( M cV c = M dV d )

w here the subscripts с and d in dicate concentrated and dilu ted solutions
respectively.
C o n v ersly, if w ater is ev aporated from a so lution, it b eco m es m ore c o n ­
cen trated , and the sam e form ula, M CV C = M dV d m ay be used in calculations.
W h en th e form ula, n = M x V is used, v o lu m e m u st b e ex p ressed in liters. B ut
the volum e m ay be expressed in any units in the equation, M CV C= M dM d.

E X A M P L E 5.2 4 C a lc u la tio n s B a sed on D ilu tio n s

Problem : 500 mL of water are added to 300 mL of 0.4 M H2SO 4 solution. Find the molarity o f the result­
ing solution.
Solution : 300 mL of 0.4 M solution contain 0.3 x 0.4 = 0.12 mol of H 2SO 4. W hen 500 mL o f water are
added, total volume will be 800 mL. The molarity is then : M = 0.12/0.8 = 0.15 M
Or we can use the equation MCVC= MdVd .
Vc = 300 mL Mc = 0.4 M Vd = 0.8 L Md = ? => 0.4 x 300 = Md x 800 => Md = 0.15 M

EXERCISE 5.22 100 mL. of 6 M HCI solution is diluted to 600 mL. What is the molar concentration of
the final solution ? 1 M

EXAMPLE 5.25 C a lc u la tio n s B a se d on D ilu tio n s

Problem : W hat volume of water must be added to 200 mL of 3 M ВаС1г solution to obtain 1 M solution ?
Solution : Let V be the volume of water to be added, then Vd = (200+V)mL
MCVC = MdVd 3 x 200 = 1 x (200+V) => V = 400 mL

EXER C ISE 5.23 How many mL of water must be evaporated from 500 mL of 0.3M NaCl solution so
that the concentration o f NaCl becomes 0.5 M ? 2 0 0 ml.

E X A M P L E 5 .26 Preparing a Diluted Solution From Concentrated One.

Problem : Describe how you would prepare 2 L of 0.7 M HNO 3 solution, starting with a concentrated HNO 3
solution that has a density of 1.4 g/mL and contains 63 % HNO 3 by mass. HNO 3 = 63 g/mol
Solution : Since the concentration of the solution to be prepared is less than the original one, this is a dilu­
tion problem. W e have Mc = ? Vc = ? Md = 0.7 and Vd = 2 L
160 Chapter 5

We can calculate M c by taking the advantage of formula : M = — — — ■ => M = ^ x 1.4 x 63 _ ^

3 6 6 MW 63

Therefore, MCVC = MdVd => (14 M) (Vc) = (0.7 M) (2 L) => Vc = 0.1 L = 100 mL
Thus, we measure out 100 mL of concentrated HNO 3 solution and dilute it to a final volume of 2 L to obtain the
desired concentration.

E X E R C IS E 5.24 How many mL of 0.5 M H 2S O 4 solution can be prepared from 20 mL of 2.5 M

H 2S O 4 solution. 100 mL

E X E R C IS E 5 .25 A 250 mL o f CH 3OH solution with a density of 0.96 g/rnL and containing 8 %
C H 3OH by mass is diluted to 2000 mL with water. Calculate the molarity of the resulting solution. 0.3 M

5:3.4 M IX IN G S O L U T IO N S
W hen tw o different solutions o f the sam e solute are m ixed the m ole n u m ­
b e r o f th e so lu te in the final so lu tio n is eq ual to th e sum o f the n u m b e r o f
m o les o f so lu tes in the so lutions b ein g m ixed. I f iq and n 2 are the n u m b er o f
m o les o f so lu tes in solutions th at are m ixed and iq is the n u m b er o f m o les o f
so lu te in th e fin al so lu tio n th e n , n j + n 2 = n fio r su b stitu tin g M V fo r n w e
o b ta in :
( Mty l + M 2 V 2 = M fVf )

E X A M P L E 5 . 2 7 C a lc u la tio n s B a se d on M ix in g S o lu tio n s
Problem : A 300 mL of 0.2 M HNO 3 solution is added to 200 mL o f 0.15 M H N 0 3 solution. Calculate
the molarity of the resulting solution.
Solution : First we will calculate the number of moles of H N 0 3 in each solution,
nj = 0.2 M x 0.3 L = 0.06 mol, n2= 0.15 M x 0.2 L = 0.03 mol, and nf = nj + n 2 = 0.03 + 0.06 = 0.09 mol
When two solutions are mixed, final volume will be 0.3+0.2=0.5 L. Then, Mf = nf / Vf = 0.09/0.5 = 0.18 M
This kind of problems can be solved by using the equation : Mj V 1 + M 2 V 2 = MfVf ,
0.2 M x 0.3 L + 0.15 M x 0.2 L = M f x 0.5 L => Mf = 0.18 M

E X E R C ISE 5.26 400 mL of 0.6 M KC 1 solution is added to 600 mL of 0.2 M KC 1 solution. What is
the molarity of the final solution ? 0.36

EXAMPLE 5.28 C a lc u la tio n s B a se d on M ix in g S o lu tio n s

Problem : W hat volumes o f 2 M and 6 M solutions o f HCI should be mixed to prepare 500 mL of a 3 M
solution? Disregard the change in the volume in mixing.
Solution : 500 mL o f a 3 M solution contain 0.5 x 3 = 1.5 mol of HCI. Let’s denote the required volume of
the 6 M solution by x; hence, the required volume of the 2M solution will be (0.5- x ) liter, x L o f a 6 M solu­
tion contain 6 x mol of HCI, while (0.5 -x) L of a 2M solution contains 2(0.5-*) mol o f HCI. Since the total
number o f moles must equal 1.5, we can write : 6 x + 2( 0.5 - £) = 1.5 => x= 0.125 L
Or M t V , + M 2 V 2 = MfVf 6 .x + 2(500-*) = 3 x 500 => * = 125 mL
Consequently, to prepare the required solution, we must take 125 mL from 6 M and 375 mL from 2 M solution
of HCI and mix them.
 Condense,(1 Phases o f Matter Liquids and Solids 161
— -------------
EXERCISE 5 . 2 7 VVIutt volum es o f 4 M and 6 VI KN(.h solutions should be mixed to obtain a 500 mL
()1; 4.8 M K N O t solution ? 300 mL and 200 mL
— _ _ — .............................................................................................................................................................................................................................

E X E R C ISE 5 . 2 8 How m any I. o f 0.25 MtL S O .i solution m ust be m ixed with 2 L o f 0.75 MI L S 0 4
to produce a solution w ith a concentratio n o f 0 .30 M? ( Hi nt: Let ,v be the v o l u m e o f 0. 25 MI b S O j
solution then final volume will be (2 + v ) I.) Is L

EXERCISE 5 . 2 9 Inwhat volum e ratios should I VI and 4 VI N a^CO ^ so lu tio n s be m ixed to obtain
1.5 VIN a T 'O j solution ? 5/1

5 .3.5 C H E M IC A L R E A C T IO N S IN S O L U T IO N S
M an y chem ical reactions o ccu r in solutions. M o st o f the experim ents you
w ill p e rfo rm in th e la b o ra to ry w ill in v o lv e th e u se o f aq u eo u s so lu tio n s.
T h erefore, it is im portant to b e able to do calculations concerning solutions.

EXAMPLE 5 . 2 9 C alculations Based on M ole - V olum e Relations

Problem : If a 200 mL o f 0.5 M HC1 solution reacts with sufficient amount of Zn, how many liters of H 2
gas at STP are produced ? Zn + 2 HC1 -> ZnCl 2 + H 2 (g)
Solution : The steps involved in the solution of the problem are :
200 mL o f 0.5 M HC1 -» ? mol HC1 —> ? mol H 2 -> ? L H 2
nHC) - m x V = 0.5 x 0.2 = 0.1 mol
Zn + 2HC1 (aq) -» ZnCl 2 (aq) + H2 (g)
2 mol 1 mol v
moj j x = 0.05 mol o f H2 is produced
0.1 mol x

The volume o f 0.05 mol H 2 at STP is : 0.05 mol x 22.4 L /l mol = 1.12 L

EXERCISE 5.30 W hat is the volum e o f 2 M HC1 that is required to react com pletely with 1 6 .2 ^ o f a lu ­
m inum according to the equation : 2A1 (s) + 6HC1 (aq) —> 2A ICB (aq) + ЗН 2 (g) 900 mL

EXAMPLE 5 . 3 0 C alculations Based on M ole - V olum e Relations

Problem : How many liters o f 0.4 M HC1 solution are required to obtain 8.2 L of H2 gas at 27°C and 570
mmHg ? Zn + 2HC1 -> ZnCl 2 + H 2 (g)
Solution : Data -> ? mol H 2 -> ? mol HC1 -» ? M HC1
n P V ^ (570/760) x (8 .2 ) = 0 25 moi
2 RT (0.082) x (300)

If 1 mol of H 2 is produced from 2 mol of HC1 1 ^

\ x = 0.5 mol o f HC1
0.25 mol of H 2 will be produced from x J-
Then, M = n/V => V = 0.5mol /0.4 mol/L = 1.25 L o f HC1 solution are required
162 Chapter 5

EXERCISE 5.31 l.
tion with sufficient amount o f Cu. Calculate the molarity o f the solution.

E X E R C IS E 5.32 C onsider the reaction

K 2C r 20 7 (aq) + 14HC1 (aq) -» 2KCI (aq) + 2C rC I 3 (aq) + 7H 20 (l) + 3C l 2 (g)
What is the volume of C l 2 al STP gas produced by the reaction of 100 mL of 0.5 M K2C r 207 with 500 mL
0.7 M HCI? 1.6 8 L
*

E XA M PLE 5.31 Calculating Atomic Weight

Problem : Consider the reaction : 2X (s) + 6NaOH (aq) -> 2Na 3X 0 3 (aq) + 3H 2 (g)
If 300 mL of 0.2 M NaOH reacts completely with X, 2.88 g of Na 3X 0 3 is produced. Calculate the atomic
weight o f X. N a= 2 3 ,0 = 1 6
Solution : 300 mL of 0.2 M NaOH -> ? mol NaOH -» ? mol Na 3X’0 3 -» MW of Na 3X 0 3 -> AW of X
nNaOH = mV = 0.2 x 0.3 = 0.06 mol
The balanced equation indicates that 6 mol o f NaOH produce 2 mol of Na 3X 0 3
| * = 0.02 mol N a 3X 0 3
0.06 x
MW = m/n = 2.88 g/0.02 mol = 144 g/mol
The atomic weight o f X is : N a 3X 0 3 = 144 = > 3 x 2 3 + X + 3 x 16 = 144 => X = 27 g/mol

EXERCISE 5.33 Consider the reaction : 3X(OH )2 (aq) + 2H 3P 0 4 (aq) -» X 3(P 0 4)2 (s) + 6 H 20 ( 1)
A student finds that 100 mL of 1 M H 3P 0 4 solution is required to completely react with 100 mL of X(OH )2 so­
lution containing 18.3 g solute. Calculate the atomic weight of X. 0 = 1 6 , H=1 8 8 g/mol

5.3.6 E Q U IV A L E N T W E IG H T AND N O R M A L IT Y
A s w e see la te r in d etail, an ele c tro n tra n sfe r o r ele c tro n sh a re ex ist in
chem ical reactions. T herefore chem ist defined a quantity o f m a tter th a t gains or
lo se s 1 m o l o f e lec tro n s in a rea ctio n . T h is q u a n tity o f m a tte r is c a lle d its
eq u iva len t m a ss o r equ iva len t (abbreviated m ^ ) . F o r exam ple N a, K , A g al­
w ay s lo se o n e e lec tro n p e r atom (o r 1 m o l o f electro n s p e r m ol o f atom ) and
p ro d u ce (+1) ch arged ion. T herefo re o n e eq u iv alen t o f these elem en ts is equal
to th e ato m ic w e ig h t o f e a c h o f th e elem en t. M g, C a, B a, S r, Z n ... alw ays
lo se 2 electro n s p e r atom . H ence one eq u iv alen t o f these elem en t is A W /2. O r
if a species gains o r loses a electrons p e r form ula u n it its eq u ivalent w ill be.
Molar mass of formula ^ \ m MW
Equivalent mass = ] m eq =

T h e valu e o f a m ay b e found by usin g the follow ing rules.

a) F o r a cid s a is the num ber o f H + p ro d u c e d b y one m olecule o f a cid
b ) F o r b a ses a is the n u m ber o f О FI' p ro d u c e d by one m olecule o f base
c) F o r salts a is the total value o f valences o f cations
 Condensed Phases o f M atter Liquids and Solids 163

d) F o r a n y substance a is the n u m b e r o f electro n s lost o r g a in e d by one

fo rm u la unit in a reaction.
T able 5.4 C om parison o f the equ ivalen ts o f various su bstan ces.

Substance a Molecular mass (g/mol) Equivalent weight (m ^ M W /a )

C/5 HCI 1 36.5 36.5 + 1 = 36.5 g
Q

§ H 2S 0 4 2 98 98 + 2 = 49 g
v>
Ш NaOH 1 40 40 + 1 = 40 g
< C a(O H )2 ,2 74 74 + 2 = 37 g
PQ
NaCl (Na+1) 1 58.5 58.5 + 1 = 58.5 g
V} N a 2C 0 3 (Na^) 2 106 106 + 2 = 53 g
h
<
v>
C aC l 2 (Ca2+) 2 111 111 + 2 = 55.5 g
A12( S 0 4)3 (Al^+) 6 342 342 + 6 = 57 g

Norm ality, or normal concentration, m ay be defined in a sim ilar fashion

to molarity. T he no rm a lity (a b b re via te d N ) is the n u m b er o f eq u iva len ts (a b ­
b revia ted £ ) o f solute p e r liter o f solution. Or

Normality = Number of equivalents of solute or I N =—

Liters of solution

The number o f equivalents, E, may be found by dividing m ass o f a sub­

stance by its equivalent mass.
e = -55- and m 4 = M W then e= m _ m.a
тщ 4 a MW/a MW

Finally the normality o f the solution is :

m -> the mass of substance (g)

N_- ^ in - ma 1 t0ta^ уа1епсУ cat‘on

M W .V J MW -» molecular weight of solute (g/mol)
V -> volume of the solution (L)
The relationship betw een normality and molarity o f a solute in a solution may
be found as follow s.
N o rm a lity o f a s o lu tio n
is a lw a y s w h o le n u m b e r )
m u ltip le o f its m o la rity . N = m 'a and n = -55— by combining these equations we may write
MW.V MW
N =M xa

N = — .a or N =Ma
f V
For e x a m p le :
1 M N aC l = 1 N N aC l, 1 M CaCl2 = 2 N CaCl2, 1 M H3P 0 4 = 3 N H 3P 0 4
 ■
WAChapter 5

EXAMPLEy<5.32 C a lc u la tin g th e E q u iv a le n t W eig h t o f a S a lt a n d its N o r m a lity

Problem : 26.7 g ol' AICI3 is added to water to make 200 mL of solution, (a) W hat is the equivalent mass
of AICI3 (b) W hat is the number of equivalent of AICI3 (c) W hat is the normality of the solution.
Solution :
(a) MWЛ1С1з = 133.5 g/mol j ^ ^m, =M
_ MWw_, m
133.5
5 =445g
a = 3 (Al3+) J a 3

( b ) E = — = _ 2 6 Л ^ _ = o _6 Cq. (c) N = — = = 3 et,/L = 3 N

m 4 44.5 g/cq V 0.2 L

EXERCISE 5$T4 72 g o f F e(N O i); is disolved in 800 m l. o f solution (a) W hat is the equivalent weight
ol L e tN ( h b (M W = ISO g/m ol) ? (b) What is the num ber o f equivalents o f FefN O .ib in the solution ? (c) W hat
is the normality o f the solution ? <090^ hni.Seq c ) l . \

E X A M P L E 5.33 C a l c u l a t i n g M a s s o f S o l u t e F r o m N o r m a l i t y v
Problem : How many grams of H 2SO 4 arc needed to prepare a 500 mL of 8 N H2S 0 4 solution ?
H2SO 4 = 98 g/mol.
Solution : 500 mL of 8 N H2S 0 4 Л ? equivalents of H2S 0 4 ? g of H2S 0 4

I. N = i = > £ = N V = 8 ^9- x 0.5 L = 4 equivalent of H £ 0 4

И . 1 equivalent of H2S 0 4 is (98/2) or 49 g

] л = 196 g o f H 2S 0 4
4 equivalents of H 2S 0 4 x

Or, the problem may be solved by converting normality to molarity first.

8 N H2S 0 4 -> ? M H 2S 0 4 -» ? mol H2S 0 4 -> ? g H2S 0 4

Since N=Ma then, M = — = - = 4 M

a 2

n —M.V —4(mol/L) x 0.5(L) = 2 mol H2S 0 4. That is (2x98) or 196 g o f H2S 0 4

EXAMPLE 5.34 C a lc u la tio n B a se d on M o la r ity - N o r m a lity R e la tio n s h ip s

Problem : W hat volume of a 0.1 M solution of H3PO 4 can be prepared from 75 mL o f a 0.75 N solution ?
Solution : First calculate the molarity o f the 0.75 N solution, and use the dilution formula to find the result.
For H3P 0 4 , a = 3 and N = M.a => M = N/a = 0.75/3 = 0.25 M
Then. Mt Vc = M j V j =i> 0.25 x 75 = 0.1 x Vd => Vd = 187.5 mL

EXERCISE 5 .Э & To what volume must 100 ml. of (1 M IKSO 4 solution be diluted to make the concen­
tration 6 N ? , 2 0 0 ml.

EXERCISE 5.3S 1low many mL of a 96 solution of ILSO.t (d = 1.84 g/mL) must be taken to prepare
I liter of a 0.25 N solution ? 6.9 ml.
 Condensed Phases o f M atter Liquids and Solids 165

N o rm a lity o r e q u iv a le n t w eig h ts are usefu l in e sp ec ially acid -b ase (or

neutralization) reactions. In an acid-base reaction equal num bers o f equivalents
o f acids and b ases c o m p lete ly re ac t w ith each o ther. T h e to p ic w ill b e d is­
cussed in c h a p te r 4 in L ycee II. K eep in m ind th at the n o rm ality o f a solution
d e p e n d s n o t o n ly on its m o larity , b u t also o n the reactio n th e so lute u n d e r­
goes.

EX# 5 /5 5 C a lc u la tin g the E c I of an A d d

Problem : CHric acid has a m olecular form ula o f H 3Q H 5O 7 . W hat is its equivalent w eight w hen used in the
follow ing reaction ? H 3C 6 H 5O 7 (aq) + 3N aO H (aq) -> ЫазСбНзО? (aq) + 3H20 (1)
Solution : Since citric acid neutralized by 3 mol of NaOH, that is 3 equivalents, then, the molecular mass
o f citric acid m ust contain 3 equivalents.

Or, a=3 m and M W „ C ,ф 7 = 192 g/mol Therefore m = Л ? 2 g /'no1 = 64 g/eq

a 3 cq/mol

EXERCISE Acetic acid CH 3COOH, a component of vinegar, reacts with Ba(OH )2 according to the
reaction: 2CH 3COOH + Ba(OH )2 —> В а(С Н зС О О )2 + 2H20 Calculate the equivalent weight of acetic acid. 60

5.4 SOLUBILITY
S om e liq u id s are m is c ib le , th at is th ey can be m ix ed in any
p ro p o rtio n s to p ro d u c e so lu tio n s. In case o f so lu tio n s o f so lid s in
liq u ids, the cap acity o f a so lv en t to d isso lv e a given so lute is o ften
lim ited at a specific tem perature.
If w e add a sm all am ount o f solid to a liquid at constant tem p er­
ature, the solid begins to d issolve and the co n cen tratio n o f the so lu ­
tion increases. A fter all the solid has dissolved, the co n centration re ­
m a in s c o n s ta n t. I f w e ad d m o re s o lid an d it d is s o lv e s , th e
co n centration w ill rise further. F inally, the added solid does n o t d is­
so lv e. N o fu rth e r ch a n g e o c cu rs in c o n c e n tra tio n . A so lu tio n in
Tem perature ( C)
w h ich no m o re so lu te can be d isso lv ed is ca lled s a tu r a te d solution.
The co n cen tra tio n o f a so lu te in its sa tu ra te d so lu tio n is ca lle d the
FIGURE 5.11G raph s h o w in g th e so lu b ility . T h e m ass o f a solid th at w ill disso lv e in 100 g(1 0 0 c m 3)
e ffe c t o f tem p e ra tu re o n th e solubili­
o f w a te r to form a saturated so lu tio n is also called the so lu b ility o f
ty o f s e v e r a l s u b s ta n c e s .
the solid. F o r exam ple the solubility o f N aC l is n early 37 g /100 cm 3
o f w ater and o f K 2C r 20 7 is 19 g/100 cm 3 o f w a te r a t room te m p era­
ture. T h e so lu b ilities o f th e se su b stan ces in d iffe re n t so lv e n ts v ary
w idely. The solubility o f a so lu te is co n tro lled p rin cip a lly b y the na­
ture o f solute a n d so lven t them selves, tem perature a n d pressure.
T he solubilities o f m o st solids increase w ith in crea sin g tem per­
a tu re as sh o w n in F ig u re 5.11. O n th e co n trary , the so lu b ilitie s o f
g a ses decrease w ith increasing the tem perature. S ee F igure 5.12. In
addition, the solubility o f a gas in a liquid is p ro p o rtio n a l to the p re s­
su re o f the gas on the su rfa ce o f the liquid. C rashing the solutes stir­
FIGURE 5.12 T h e te m p e r a tu r e
d e p e n d e n c e o f solubilities o f a solid ring o r shaking the solution increase the rate o f dissolving b u t do not
a n d a g a s e o u s s u b s ta n c e affect the solubility o f a given solute.
166 Chapter 5

EXAMPLE 5 .3 6 C alcu latio n s B ased on the S olubility

Use the following solubility curve to answ er Examples. 5.35, 5.36,
5.37, 5.38 and Exercises 5.38.
Problem: A solution of X is prepared by dissolving 25 g of X in
200 g o f H20 at 20°C. How many more grams o f X m ust be dis­
solved in the solution so that it becomes saturated ?
Solution : Figure indicates that 15 g of X can be dissolved in 100
g of H20 to form a saturated solution at 20°C.
If 100 g of H20 can dissolve 15 g of X л
! ! j (<C) .. . \ x = 30 g o f X
j | i j У- 200 g of H20 can dissolve x J
20 30 40 50 Then 30 - 25 = 5 g of X must be added to saturate the solution.

EXAMPLE 5 . 3 7 C alcu lation s B ased on the Solubility

Problem : At 30°C a saturated solution of X is prepared by using 300 cm 3of water. And then it is heated to
50°C. How many grams of X must be added to saturate the solution at 50°C ?
Solution: The curve shows that the solubility of X is 20 g/100 g H20 at 30°C and is 40 g/100 g H20 at
50°C
Then, at 30°C 300 cm of water can dissolve : — — x 300 g H 20 = 60 g of X
100 g H20

at 50°C 300 cm water can dissolve : --------------- x 300 g H 2O = 1 2 0 g o f X

1 0 0 g H 2O

In that case, 120 -*60 = 60 g of X must be added.

EXAMPLE 5 .3 8 C alcu lation s Based on the Solubility

Problem: At 40°C a saturated solution of X is prepared with 200 g of H20 . And then, it is cooled to 20°C.
How many grams of X willcrystallize out of the solution ?
Solution: From the given curve
at 40°C 200 g of H 20 can dissolve 3 0 g o fX x 200 = 60 g of X
100 g of H 20

at 20°C 200 g of H 2О can dissolve 15 g o f X x 200 = 30 g of X

100 g of H 20

In that case, when the temperature is reduced from 40°C to 20°C,

60 - 30 = 30 g of X will turn back to solid phase.

EXAMPLE 5 . 3 9 C a lcu lation s B ased on the S olubility

Problem : At 50°C, 280 g o f a saturated solution of X is prepared. If it is cooled to 20°C, how many
grams of X will precipitate ?
Solution: At 50°C the solubility of X is 40 g/100 g H20 from the curve. It means that 40 g of X + 100 g
of H 20 = 140 g solution. Then, 280 g o f solution contain 200 g of H20 and 80 g of X. W hen a solution is
cooled, the amount of water remains the same, but the mass of solute dissolved in the solution decreases.
 Condensed Phases o f Matter Liquids and Solids 167

Al 20°C 100 g of H20 can dissolve 15 g of X

| x = 30 g of X
200 g of H 20 can dissolve x
There were 80 g of X initially. In that case 80 - 30 = 50 g of X will precipitate.

EXERCISE §|Q8 Answer the following questions for the substance X whose solubility versus tem pera­
ture curve is given in example 5.35. a) W hat is the maximum grams of X that can be dissolved in 250 g o f water
at 30°C ? b) A 400 mL of H20 at 40°C is saturated with X and then cooled to 10°C. How many grams of X
will crystallize out of the solution ? c) A 480 g of saturated solution of X at 30°C is heated to 50°C. How many
grams of X are needed to saturate the solution at 50°C? d) How many grams of X can be dissolved at 50°C in a
10 % of 200 g o f X solution, e) When a quantity of saturated solution of X at 10°C is heated to 40°C, 10 g of X
must be added to saturate the solution. W hat is the volume of water in the solution ? 0 At 40°C, 10 g of X are
dissolved in 50 g of water. If the solution is cooled, at which temperature docs the solid start to precipitate ?
a)S0 b )80 c)8 0 d)S 2g e )5 0 m L f ) 3 0 ° C

EXERCISE 5.39 The solubility of Na 2S 0 4 at ? 0 °C is 20 g Na 2S0 4/100 g H 20 . What is the percentage

com position o f the saturated solution of Na 2S 0 4 at 30°C ? 16.7%

5 .4 .1 SE PA R A TIO N S OF SO L U T IO N S IN T O
T H E IR CO M PO N EN TS
Solutions can be separated into th e ir com pon ents b y m eans o f
f i l t r a t i o n , d i s tilla tio n , c r y s t a l l i z a t i o n , and e x t r a c t i o n
so forth so on.
(a) F i l tr a tio n :
A m ix tu re o f tw o solids can be sep arated by filtration. I f one
o f the solids is so lu b le b u t the o th e r is n o t so lu b le in a solvent,
the m ix tu re is added to the so lv e n t and a tw o -p h ased m ix tu re is
obtained. T he undissolved com p o n en t can be separated by filtra­
tion. T he undissolved solid p articles are retained by the filte r p a ­
p er. T he o th e r so lid d isso lv e d in so lv e n t ca n b e o b ta in e d by
ev aporating the filtrate. F o r exam ple, sand and salt can b e sep ar­
ated u sin g w ate r as a solvent. S alt is soluble in w a ter b u t san d is
not.
(b ) D is tilla tio n :
Distillation is а т | 1е d ifferen ces in bo ilin g points o r solub ilities are u sed to separate
process o f converting a liquid , , . T. , , , ,
into the vapor, then cooling the the so lu tio n s. If b o th the so lid so lu te and ltq u td so lv en t are to b e ob-
vapor to the pure liquid. It is tain ed , the sim ple d is tilla tio n c an be u sed to sep arate the co m p o n e n ts
used for separating a pure liquid o f the solution. T h e liquid evaporates during the distillation and the v apor
from a mixture. is co n d e n se d as sh o w n in F ig u re 5.13. T h e solid re m ain s b eh in d as a
resid u e. S o lu tio n s in w hich b o th so lute and so lv e n t are liq u id s can be
se p a ra ted b y a p ro cess called f r a c tio n a l d is tilla tio n .T h is m e th o d o f
sep aration is based on the difference in bo ilin g points o f the liquids.
(c) F r a c tio n a l C r y s ta lliz a tio n :
S om e solids have h ig h so lu b ilities in h o t w ate r b u t lo w so lu b ilities
in cold w ater. U sing this fact the m ix tu re o f solids c an b e separated into
168 Chapter 5

its co m p o n en ts. C o n sid er the m ix tu re o f potassiu m n itrate, K N O 3, and table

salt; N aC l is so lu b le in h o t w a ter b u t o n ly m o d e ra tely so lu b le in co ld w ater.
S ec F ig u re 5.14. O n the o th er hand, K N O 3, is quite soluble in cold w a te r and
extrem ely so lu b le in hot w ater. W hen a h o t solution co n tain in g the m ixture o f
K N O 3 and N aC l is cooled, the K N 0 3 w ill crystallize o u t o f solution w hile the
tab le salt rem ain s d issolved. T h e p ro cess is called fractional crystalliza­
tio n .
S u p p o se you have 80 g o f K N 0 3 w h ich is co n tam in a ted w ith 15 g o f
N aC l. T o separate the K N O 3 from this m ixture w e first dissolve the m ixture in
T em perature (°C)
50 m L o f w a te r at 75°C , (A t 75°C 80 g o f K N O 3 and 15 g o f N a C l c an d is­
solved in 50 m L H 20 ) and then gradually cool the solution to 0°C. A t this tem ­
p eratu re 5 0 m L o f w ater can d issolve 6 g o f K N O 3 and 17 g o f N aC l. F inally
FIGURE 5.14 The dif­ (80-6) o r 74 g o f K N O 3 w ill separate from the solution, b u t all o f the N aC l re­
ference in solubilities of
m ain in the solution. In this m anner, about 90 % o f the o rig in al K N 0 3 can be
K N 0 3 and NaCl at 75°C
o b tained in the p u re form . T he K N 0 3 crystals can be separated from the solu­
and 0°C enables us to tion b y filtration.
separate one of these
(d) Extraction :
substances from the so­
lution containing both T he solubility o f a solute in tw o d ifferen t solvents m ay be different. T his
substances. The p ro ­ fact can be used as the basis for the separation. F o r exam ple, w ater and carbon
cess is called fractional
tetrachloride m ust separate into tw o distinct layers after they are m ixed. Iodine
crystallization.
is 85 tim es so lu b le in CC14 th an H 20 b u t salt is so lu b le in w ate r b u t n o t in
CC14. Iodine and salt can be separated from th eir aqueous solution by m eans o f
the extraction technique.

5.5 ELECTRIC NATURE OF MATTER

AND IONIC EQUATIONS
M any su b stances d issolve in w ater to giv e a so lu tio n that con d u cts elec­
tricity . S u ch su b sta n c es arc c alled electrolytes. F o r a so lu tio n to co n d u ct
electricity , the so lution has to contain ions. T herefo re w e say that electrolytes
are the substances that p ro d u ce ions in their solutions. A n exam ple o f electro­

щ и lyte is so d iu m chloride. N aC l disso lv es in w a te r to g iv e N a + and CL ions that

are able to m o v e freely th ro u g h o u t the solution. T h ese freely m o v in g io n s are
responsible fo r the conductivity o f the solution.
M o st o f th e electrolytes are substances w hich are m ade up o f ions (ionic
com pounds). W hen added to w ater, they dissociate into th eir com p o n en t ions.
E x a m p le s:
NaCl (s) -> Na+ (aq) + CL (aq)
Ca(NC>3)2 (s) -» Ca2+ (aq) + 2NO 3 (aq)
O n th e o th e r hand, som e su b stan ces, su ch as sugar, alcohol d isso lv e in
w a te r b u t d o n o t pro d u ce ions (they retain th e ir m o le c u la r structure). T hese
substances are called nonelcclrolytes o r m olecular com pounds.
C 12H 22O 11 (s) - » C 12H 22O 11 (aq)
FIGURE 5.15 A s i m ­ sugar sugar in solution
p le d e v ic e th a t c a n b e T h e so lu tio n s o f n o n elec tro ly te s do n o t co n d u ct electricity . See F ig u re
u s e d to d if fe r e n ti a te
5 .1 5 . N o n e le c tro ly tes are m ad e up o f n e u tra l m o lecu les. T h ere fo re th ey are
e le c tr o ly te s a n d n o n e ­
u su ally referred to m o lecu lar substances.
le c tr o ly te s .
 Condensed Phases o f M atter Liquids and Solids 169

E X A M P L E 5 . 4 0 Writing- Ion ic E qu ation s

Problem : The solids listed below dissolve readily in water to give conducting solutions. W rite an ionic
equation for each substance.
a) Na 2S 0 4 Sodium sulfate b) NH 4C1 Ammonium chloride
c) (NH 4)2 C 0 3 Ammonium carbonate d) N aH C 0 3 Sodium bicarbonate
e) CuCl 2 Cupric or copper(II) chloride OKI Potassium iodide
Solution ;
a) N a ^ C ^ (s) —> 2Na+ (aq) + SO2' (aq) b) N H 4C1 (s) -> N H ^(aq) + Cl'(aq)
c) (NH 4)2 C 0 3 -> 2NH 4 (aq) + C 0 2‘(aq) d) N aH C 0 3 (s) Na+ (aq) + H C 0 3 (aq)
e) CuCl 2 (s) ■ Cu
~ - 2+ (aq) + 2СГ (aq) 0 KI (s) К (aq) + г (aq)
5 . 6 S O N C O N C E N T R A T I O N

O ne m o le o f a m o le cu lar solid su ch as su g a r furnishes ju s t one m o le o f

solute p articles (neutral m olecules). O ne m o le o f an ionic co m p o u n d , h o w ev ­
er, supplies m ore than one m ole o f solute particles(ions). T h e co n cen tratio n o f
ea c h io n m ay be calculated from the m o larity o f the solute and e q u atio n th at
show s th e d isso cia tio n o f the solute. C o n sid er a 0.2 M so lu tio n o f alum inum
chloride, A1C13 . T he equation fo r the dissociation is
AICI3 (s) A l3+ (aq) + ЗСГ (aq)
I f th e d isso c ia tio n is com p lete, o n e m o le o f alu m in u m io n s and th ree
m o les o f chlo ride ions are in solution fo r each m ole o f A1C13 dissolved. T h e re ­
fore, a 0.2 M AICI3 solution has an A l3+ ion co n centration o f 0.2 M , and a Cl"
ion co n cen tration o f 0.6 M .O r
AICI3 (aq) -> A l3+ (aq) + ЗСГ (aq)
1M 1M 3M
0.2 M 0.2 M 0.6 M
G en erally b rackets are used to in dicate the m olarity o f an ion. T h en , w e m ay
w rite [A l3+] = 0.2 M and [C1"] = 0 .6 M .

E X A M P L E 5 . 4 1 C alcu latin g Ion C on centration s

Problem : 32.5 grams o f FeCl 3 (s) is dissolved in water to form 100 mL of solution. Calculate the molarity
of Fe3+ and СГ ions in the solution. FeCl 3 : 162.5 g/mol
Solution: 32.5 g o f FeCl3 -> ? mol FcCl3 -> ? mol Fe3+ and ? mol СГ н> ? M Fc3+ and ? M Cl"

I. - 32.5 g _ 0 2 mQl II. FcCl3 (s) Fe3+ (aq) + 3C1" (aq)

' 3 162.5 g/m ol 1 mol 1 mol 3 mol
0.2 mol 0.2 mol 0.6 mol

III. [Fe3*] = — = — - ol = 2 M [Cl ] = — = 0 6 mo1 = 6 M

V 0.1 L V 0.1 L

EXER C ISE 5.40 21.2 g N a 2C 0 3 is dissolved in water to form 800 mL of solution. Calculate the mo­
larity of each ion in the solution Na 3C 0 3= 106 g/mol / Na+]=0.50M [ C ()j'j =0 .2 5 M
170 Chapter 5

E X A M P L E 5 . 4 2 U n d erstan d ing Ion C oncentration Concept

Problem : How many grams o f Al2( S 0 4)3 arc needed to prepare 300 mL of solution in which the S 0 4‘ ion
concentration is 0.2 M ? Ai2(S 0 4)3=342 g/mol
Solution : 300 mL of 0.2 M SO f -> ? mol SOZ 4 -> ? mol A12(S 0 4)3 -» ? g A12(S 0 4)3

nso2~ = 0.2 x 0.3 = 0.06 mol A12(S 0 4)3 (s) ^ 2A13+ (aq) + 3 S 0 4' (aq)
1 mol 3 mol 1
x mol 0.06 mol j * = 0.02 mol o f A12( S 0 4)3

The mass of 0.02 mol of A b ( S 0 4)3 = 0.02 mol x 342 g/mol = 6.84 g

EXER C ISE 5.41 How many grams of (NH4)2SCL arc needed to prepare 200 mL of solution in which
the molarity o fN H /j ion is 2 M ? (NH 4) 2S Q 4 = 132 g/mol 26.4 g

EXER C ISE 8 f t 2 32.8 g of X (N 0 3)? are used to prepare 300 mL of solution in which the molarity of
NOj ion is found to be 0.8 M. What is the atomic weight of X '.’ N=14, 0=16 40 g

EXAMPLE 5 .4 3 Calculating Ion C oncentration After M ixing Solutions

Problem : A 200 m l, o f 0.3 M MgCl2 solution is mixed with 300 mL of 0.2 M A1C13 solution. Calculate
the molarity of each ion in the resulting solution.
Solution :
n MgCt2 = 0.3 x 0.2 = 0.06 mol nAici 3 = 0.2 x 0.3 = 0.06 mol
M gCl2 (s) -» Mg2" (aq) + 2СГ (aq) A1C13 (s) -» A l3+ (aq) + ЗСГ (aq)
1 mol 1 mol 2 mol 1 mol 1 mol 3 mol
0.06 mol 0.06 mol 0.12 mol 0.06 mol 0.06 mol 0.18 mol
The number o f moles of each ion in the final solution is:
nMg2+ = 0.06 mol nA|3+ = 0.06 mol net* = 0.12 + 0.18 = 0.3 mol
The volume of the mixture is 200 ntL + 300 mL = 500 mL = 0.5 L. The molarity o f each ion will be :

[M g2"] = 0-06 mo1 = 0 .1 2 M [A M i™ l = ().12 M fCl"] = М ™ Ё . = 0.6 M

0.5 L 0.5 L 0.5 1.

E X E R C ISE 5 . 4 3 200 mL of 0.1 M N aN 03, 200 m l. of 0.2 M C a (N 0 3)2 and 0.02 mol AI(N 0 3)3 are
mixed and the resulting solution is diluted to 1 L. Calculate the concentration of each ion in the solution.
[ N a + 1=0.02,M, / Cu~ + 1 - 0 . 0 4 M , / Л /?+j= 0.0 2M / N O j 1 = 0 . 1 6 $1

E X E R C IS E 5 . 4 4 C onsider CaCI 2 and A1C13 solutions with equal molar concentrations. When 1 L of
С аС Ь and 2 L of A1C13 solutions arc mixed, the |A1U | in the resulting solution is 0.5 M. What is the [Cl ] in
the solution ? 2 M

E X A M P L E 5 . 4 4 C alcu lation s Based on Ion C on centration s

Problem : W hat volume of 0.4 M CaCl2 sglution must be mixed with 3 / t o f 0.2 M FeCl3 solution .so that
the CL ions concentration in the resulting solution is 0.68 M?
 Condensed. Phases o f M atter Liquids and Solids 171

Solution: ncaCl2 = 0.4 x V = 0.4 V mol nFeCij = 0.2 x 3 = 0.6 mol

CaCl2 (s) -> Ca2+ (aq) + 2СГ (aq) FeCl3 (s) -> Fe3+ (aq) + 3C1‘ (aq)
1 mol 2 mol 1 mol 3 mol
0.4 V mol x mol 0.6 mol x mol
= 0.8 V mol o f СГ
x x = 1.8 mol o f СГ

The total mol o f СГ = (0.8 V + 1.8) mol [Ci ] _ (0.8 V + 1.8) mol _ 0 6g м => у - 2 L
VT = (V+3) L -" T V + 3 ) L ,.,

EXERCISE 5.45 W hat volum es o f 1 M NaCl and 5 VI of С аС Ь solutions m ust be m ixed to obtain 500
mL o f solution in which [Cl"]=3 M? 3 0 0 m L a n d 2 0 0 mL

EXERCISE 5.46 250 mL of 0.2 M CaCl2 and 250 mL of unknown concentration of FeCl3 solutions arc
mixed. If the[СГ] in the resulting solution is 0.8 M, calculate the molarity o f A1C13 solution ? 0. 4 M

EXERCISE 5.47 300 mL of 0.2 M Ba(OH)2, 600 mL of 0.4 M NaOH, and 3.42 g of X(OH )2 arc mixed
and then the resulting solution is diluted to 1000 mL. If the [OH' ] =0.4 M in the final solution, calculate the
atomic weight of X. 0 = 1 6 , H=1 137 g/mol

5.7 SOLUBILITY RULES

S o m e c o m p o u n d s are very so lu b le in w ater, w h ereas o th ers do n o t d is­
so lv e to any ap p rec iab le extent. T h e w o rd , so lu b le, d o es n o t h av e an e x ac t
m ean in g . H o w ev er, fo r p ra ctica l p u rp o ses su b sta n ce s m a y b e c la ssifie d in
th re e gro u p s acco rd in g to th eir solubilities. S oluble, m o d e rate ly so lu b le and
n e g lig ib ly so lu b le o r insoluble. I f a su b sta n ce h a s a so lu b ility m o re than 0 .1
m o l/L a t 2 5 °C it is a ssu m ed to b e so lu b le. The su b sta n c es w h o se so lu b ilities
a re 0.01 to 0.1 M are sa id to be m o d erately soluble, a n d those w h o se so lu b ili­
ties are b elo w 0 .0 1 M are referred to as being negligibly so lu b le o r insoluble.
S o m e q u alitativ e generalizations concern in g the so lubilities o f su b stances are
g iv en in T ab le 5.5.
T A B L E 5 .5 Solubilities o f Som e C om pounds in Water

MAINLY W A T E R -SO L U B L E MAINLY W A T E R -IN S O L U B L E

NO 3 A ll n itra te s are so lu b le. S2" A ll su lfid es are in so lu b le e x ce p t

those o f the I A and П A e le m en ts and (N H 4 ) 2 S .
CH 3 C O O ' A ll a cetates a re soluble.
СЮ 3 A ll c h lo ra te s a re so lu b le. 2-
CO3 A ll c a rb o n a te s are in so lu b le e x c e p t th o se
o f the I A and (N H 4 ) 2 C 0 3 .
СГ A ll c h lo rid es are so lu b le e x c e p t
A gC l, H g 2 C l2, and PbC l2 . 2 _
SO 3 A ll su lfite s are in so lu b le e x c e p t th o se o f the
B r' A ll b ro m id e s are solu b le e x ce p t I A and (N H 4 ) 2 S 0 3.
A gB r, H g 2 B r2, P bB r2, and H gB r2.
3 .
P04 A ll p h o sp h a tes are in so lu b le e x c e p t th o se
Г A ll io d id es are so lu b le e x ce p t o f the I A and (N H 4 ) 3 P 0 4 .
A g l, H g 2 I2 , P b l2, and H g l2 .
2- OH" A ll h y d ro x id es are in so lu b le e x ce p t th o se
S04 A ll su lfa te s are so lu b le e x ce p t o f the I A and B a(O H )2, S r(O H )2, and C a (O H )2 .
C a S 0 4, S r S 0 4, B a S 0 4, P b S 0 4,
H g 2 S 0 4, and A g 2 S 0 4 .
172 Chapter 5

5.8 PRECIPITATION REACTIONS

B oth lead (II) nitrate, P b ( N 0 3)2, and sodium sulfate, N a 2 S 0 4, are soluble
in w ater. W h at w ill hap p en if w e m ix these tw o so lutions ? E a ch o f th ese su b ­
stances is p resen t in solution in the form o f separated ions.
P b ( N 0 3)2 (s) -> P b 2+ (aq) + 2 N 0 3 (aq)
N a 2S 0 4 (s) —> 2 N a+ (aq) + S Q 4' (aq)
T h e oppo sitely charged ions com ing from d ifferen t solutions m ig h t c o m ­
b in e to form co m p o u n d s. (P b 2+ and S O 2', N a + and N 0 3 ions). T h e la st p a ir
N a+ and N 0 3 p ro d u ces a co m p o u n d th a t is soluble in w ater. B u t the c o m b in a­
tio n o f th e first p a ir P b 2+ and S O 2' p ro duces an in so lu b le su b stan ce, P b S 0 4.
T h e n , th is su b stan c e is p ro d u ced as a solid. The fo rm a tio n o f a so lid fr o m a
solution is called p r e c ip ita tio n . T h e eq u atio n fo r the p re c ip ita tio n m ay be
w ritten as e ith e r in m o lecu la r form
P b ( N 0 3)2 (aq) + N a2S 0 4 (aq) -> P b S 0 4 (s) + 2 N a N 0 3 (aq)
o r in io n ic form .
P b2+(a q )+ 2 N 0 3 (aq)+2N a+ (a q )+ S 0 42' (aq) -> P b S 0 4 (s)+ 2N a+ (a q )+ 2 N 0 3 (aq)
T h is is c alled a co m p lete io n ic e q u a tio n . H o w ev er, th e tw o ions N a +
and N 0 3 do n o t p lay any role in the reaction. T h ere fo re th ey are called sp ec ­
ta to r ions. C an cellin g the sp e c ta to r io n s fro m th e c o m p le te io n ic e q u atio n
g iv e s th e n e t io n ic eq u a tio n
P b2+ (aq) + S 0 4' (aq) -> P b S 0 4 (s)
T h e b a la n c ed n et ionic e q u atio n in clu d es o n ly th e sp e cies th a t actu ally
p lay active role in the reaction. (P red o m in a n t r e a c tin g sp ecies)

FIGURE 5.16 Precipitation of lead sulfate.

E X A M P L E 5 .45 W r itin g N et I o n ic E q u a tio n s

Problem: Write the net ionic equation for the formation of a precipitate of insoluble barium sulfate, B a S 0 4,
when an aqueous solution of barium chloride, BaCl2, is mixed with an aqueous solution of sodium sulfate,
N a 2S 0 4.
-
Solution : In terms of the molecular formulas, the equation is:
BaCl2 (aq) + N a 2S 0 4 (aq) -> B a S 0 4 (s) + 2NaCl (aq)
 Condensed Phases o f M atter Liquids and Solids 173

The corresponding ionic equation is :

Ba2+(aq) +2Cl'(aq) +2N a+ (aq) + S 0 24 (aq) -> B a S 0 4 (s) + 2Na+ (aq) + 2СГ (aq)
Cancelling the spectator ions (Na+ and СГ) gives the net ionic equation :
Ba2+ (aq)+ S 0 24 (aq) ~> BaSO 4 (s) ' '

E X E R C IS E 5.48 Write the net ionic equations lor the following reactions.
a) MgCU (aq) + 2A gN O , (aq) -> 2AgCl(s) + M g(N 03b (aq)
b) 3NaO! I (aq) + AICI 3 (aq) Al (ОН) 4 (s) + 3NaCl (aq)

E X A M P L E 5 .4 6 C a lc u la tio n s B a sed on th e M ix tu r e o f A q u e o u s S o lu tio n s

Problem : When 1 liter of 0.4 M NaCl solution is mixed with 1 liter of 0.1 М P b (N 0 3)2 solution, PbCl 2
precipitates a) Write the complete ionic equation and net ionic equation for the reaction, b) Which substance is
in excess in the precipitation reaction ? How many moles of РЫ 2 will precipitate ? c) Calculate the molarity of
each ion remaining in the solution at the end of precipitation.
Solution : a) 2Na+ (aq) + 2 СГ (aq) + Pb2+ (aq) + 2 N 0 3 (aq) -> PbCl2 (s) + 2Na+ (aq) + 2 N 0 3 (aq)
The net ionic equation is obtained by eliminating the spectator ions from the complete ionic equation, that is.
Pb2+ (aq) + 2СГ (aq) -* PbCl2 (s)
b) Step I. Calculate the number of moles of each ion in the final solution assuming that the precipitation does
not occur.
iiNaCi = 0*4 mol/L x 1 L — 0.4 mol NaCl (s) —> Na+ (aq) + Cl (aq)
0.4 mol 0.4 mol 0.4 mol
прЬ(х о з )2 = mol/L x 1 L = 0.1 mol РЬ(ЫОз)2 (s) -» Pb2+ (aq) + 2 N 0 3 (aq)
0.1 mol 0.1 mol 0.2 mol
Step II. W rite the ionic equation and determine the limiting or excess ion.
moles of snccies : Pb2+ (aq) + 2CL (aq) —» РЬСЬ (s) The inspection o f the coefficients o f the equation
Before reaction : 0.1 0.4 0 indicates that 0.1 m ol Pbi+ can only com bine
Change in reaction : -0.1 -0.2 +0.1 w ith 0.2 mol o f СГ. (0.4-0.2=0.2 mol) o f СГ is
A lter reaction : 0 0.2 Q. 1 ex cess. T h e re fo re P b 2+ is lim iting. (-) sign is
(negligible) (excess) used to indicate the consum ption and (+) sign to
We see that 0.1 mol of PbCl 2 will be precipitated. indicate production o f substances.

c) The solution at the end o f precipitation now contains 0.4 mol of Na+, 0.2 mol of CL, 0.2 mol of N 0 3 and
negligible quantity of Pb2+. The molarities of these ions arc :

[Pb ] = —= 0 or negligible fCl ] = ^ - = 0 . 1 M

2 2
[Na+J = M = 0.2 M [N 0 3 | = ^ = 0 .1 M ‘
2 . 2 _______________

E X A M P L E 5.47 C a lc u la tio n s B a se d on th e M ix tu r e o f S o lu tio n s

Problem : When 1 liter of 0.2 M РЬ(ЫОз)2 and 0.5 liter of KI solutions arc mixed, Pbl 2 precipitates. If the
molarity o f the I" ions is 0.4 M after precipitation, what is the concentration of KI ?
'i
174 Chapter 5

Solution : Since the (I'J = 0.4 M after precipitation, we deduce that Pb2+ ions act as limiting and Г ions as
excess reagents in the precipitation reaction. Then we can write :
np (in KI) = П[- (used in precipitation reaction) + n£- (excess in 1.5 L final solution)
nj- (excess) = M x V = 0.4 mol/L x 1.5 L = 0.6 mol
The number o f moles o f Г used in precipitation reaction is :
n l>b(N03)2 = mo'/L x 1 L - 0.2 mol => 0.2 mol Pb2+ Pb2+ (aq) + 2Г (aq) -4 РЫ 2 (s)
1 mol 2 mol 1
• 0.2 mol x ) X = <14m0i

So the number of moles of Г in KI solution equals : 0.6 mol (excess) + 0.4 mol (used) = 1 mol

1 mol Г is present in 1 mol KI, then, the molarity of KI is : M = — = i~—9.1. = 2 M

V 0.5 L

Another approach to the solution of the problem is given below. Assume that the molarity of KI solution is
x mol/L and follow the procedure in Example 5.46.
ni>b(N03)2 = 0:2 M x 1 L = °-2 ITwl r? P b(N 0 3)2 (s) -+ Pb2+ (aq) + 2 N 0 3 (aq)
0.2 mol 0.2 mol 0.4 mol
П]<1 = xM x 0.5 L = 0.5x mol => KI (s) —» K+ (aq) + I" (aq)
0.5x mol 0.5jc mol 0.5x mol
m oles Pb2+ (aq) + 2Г (aq) —> РЫ 2 (s)
Before reaction : 0.2 0.5x 0
Change in reaction : -0.2 -0.4__________+0.2
After reaction : 0 (0.5x - 0.4) +0.2
(negligible) (excess)
Since (0.5x - 0.4) mol of excess Г ions produces a 0.4 M concentration in 1.5 L solution, then, the value of x
will be :
|I ] := — => 0.4 = °-5л' ~ ° -4 => x = 2 Or, KI solution is 2 M
V 1.5

EXER C ISE 5.49 When 200 mL. of 0.4 VI КтСгО j solution is mixed with 300 mL of 0.6 M SrC b solu­
tion, SrCrO^ precipitates. Calculate the concentration oLeaeh ion after precipitation.
IK + I-0.32M , jC l' j=0.72M , / S r 2 + 1=0.2 M . IC rO *' {^ n e g lig ib le

EXERCISE 5.50 When 200 mL of 0.2 VI F e(N 03h and 300 mL of unknown concentration of Sr(OH )2
solutions were mixed, Fe(OH)t precipitated. If the hydroxide ton concentration after precipitation in the final so­
lution is measured to be 0.06 VI, what was the molarity o f StlO H js solution ? What was the mass of Fc(OH )3
precipitated ? F e (O llh = 107 0 . 2 5 M . 4. 2S g

EXER C ISE 5.51 When 100 mL of 1.2 M Na 3PO.t and an unknown volume of 0.24 M СаСЬ solutions
are mixed, a negligibly soluble substance, C a 3(PO.|) 2, precipitates, lf the |P O , |' = 0.04 N1 after precipitation
(a) find the volume of СаС Ь solution, (b) Mow many mg of Ca 3(PO .t)2 tire precipitated ? (c) What is the molar
concentration of each ion remaining in the solution after the precipitation reaction has ended ? Ca-yfPO./)? = 310
a)58(> mL 0 )4 8 .1 g
 Condensed Phases o f M atter Liquids and Solids 175

SOM E NEW TERM S

A lloy is a m ixture o f two or m ore metals when 1 mol of liquid is converted to 1 mol of vapor at
A nion is a negative ion constant temperature and pressure.

A queous solution is any solution having water N orm ality is the num ber o f equivalents per liter
as the solvent of an acid, or a base or other reactant.

C ation is a positive ion Phase is a homogeneous region within a sample.

C oncentrated solu tion is any solution with a S atu rated so lu tio n is one that contains the
large ratio of the amounts of solute to solvent. maximum quantity of solute that is normally possi-
Ые.
D ilute solution is any solution with a small ra­
tio of the quantities of solute to solvent. S o lu te is a substance dissolved in a solvent to
make a solution.
Ionic com pound is a com pound com posed o f
positive and negative ions (e.g. NaCl, Ca.C\f) Solvent is usually a liquid, into which the solute
is dissolved to make a solution.
M eltin g (or fu sion) is a process in which a
solid changes into liquid. Supersaturated solution is any solution con­
taining more solute than a saturated solution would
M o la rity (or m olar co n cen tra tio n ) is the
hold at a given temperature.
number of moles of solute per liter of solution.
Unsaturated solution contains less solute than
M olar heat o f fusion is heat absorbed when 1
the solution is capable o f dissolving under the given
mol of a solid melts to give 1 mol of liquid at con­
conditions.
stant temperature and pressure.
Vapor pressure is the pressure exerted by the va­
M olar heat of vaporization is heat absorbed
por above a liquid.

R E V IE W Q U E S T IO N S
5.1 Define the following terms 5.6 W hy does the vapor pressure o f a liquid in­
a) Melting or fusion b) M elting point crease with increasing temperature?
c) Freezing d) Freezing point 5.7 At 20 °C the vapor pressure o f benzene is 75
e) Evaporation f) Condensation mmHg and that of toluene is 50 mmHg. Which hydro­
g) Boiling h) Boiling point carbon is expected to have a higher boiling point at at­
i) Sublimation j) Deposition mospheric pressure?
5.2 W hat kind of relationship is there between 5.8 Before the refrigerator was invented, butter and
the boiling points and the molar heat o f vaporization milk were stored in porous clay pots standing in H 20 .
of substances? Why would such a system keep the contents cool even
5.3 W hat is the difference betw een evaporation on the hottest day?
and boiling ? Explain.
5.9 W hy is the boiling point o f a substance more
5.4 W hich one o f the following affects the boiling pressure dependent than its melting point ?
point of a liquid?
5.10 W hich will cause severe bum ? W ater at
a) mass of the liquid b) purity of the liquid 100°C or steam at 100°C. Explain.
c) outer pressure d) the capacity o f the heater. 5.11 W hat is vapor pressure ? W hat factors affect
5.5 For m ost m olecular substances, the heat of the equilibrium vapor pressure?
vaporization is several times larger than the heat of fu­ 5.12 Consider a cylinder containing a liquid in dy­
sion. Explain this on the basis of structure and forces. namic equilibrium with its vapor at a certain tempera­
 176 Chapter 5

ture. If the volum e o f the vapor over the liquid is solution. Explain why NaCl or СаС1г are employed to
halved by pushing the piston down at the same tem ­ melt ice on roads in winter.
perature, the vapor pressure remains unchanged. Why? 5.21 Com pare the boiling points o f the following
5.13 The vapor pressure o f a liquid increases with substances under indicated pressure
increasing tem perature. Explain this in terms o f mo­ substance pressure
lecular theory of matter.
pure water 1 atm
5.14 W hat is the adventage o f cooking food in
pure water 0.9 atm
pressure cookers ?
0.1M sugar solution 1 atm
5 .1 5 W hy is the boiling tem perature for w ater
lower at A gn than at Izmir? 0.1M NaCl sqlution 1 atm

5.16 W hat argument can be given that solid naph­ 0.1M NaCl solution 0.9 atm
thalene has a measureable vapor pressure at room tem­ 0.1M СаС1г solution 2 atm
perature? 5.22 Define the following terms
5.17 W hat is an electrolyte ? Explain. a) solute b) solvent c) dilution
5.18 The conductivity of a 0.01M CH 3COOH so­ d) saturated solution e) supersaturated solution
lution is greater than 0 .0 1M sugar solution but it is
f) solubility g) percentage concentration
less than 0.01M NaCl solution. W hat conclusion can
h) molarity i) normality
you draw from this ?
5.23 W hat factors affect the solubility o f a) solids
5.19 W rite the equation for the reaction that oc­
in liquids b) gases in liquids.
curs when each of these electrolytes is dissolved in wa­
ter. % 5.24 Explain the follow ing term s, and indicate
where each is used ?
a) Lithium hydroxide b) Aluminum chloride
a) distillation b) fractional distillation
c) Potassium sulfate d) Sodium nitrate
it c) fractional crystallization
e) Ammonium iodide f) Potassium carbonate
5.25 W hat is precipitation? How do you write the
5'.20 Com pare the freezing points of pure water,
net ionic equation for a precipitation reaction ?
>*1M sugar solution, 1M NaCl solution and 1M СаС1г

R E V IE W P R O B L E M S
Phase C h a n g e s
5.26 Calculate the quantity of heat accompanying boiling temperatures of alcohol is -114°C and 78°C
to (Refer to Table 5.1.) respectively, (for alcohol, d=0.8 g/mL, c=0.6 cal/g°C,
a) melting 25 g of ice at 0°C Lv=204 cal/g)

b) condensation of 100 g of steam at 1Q0°C d) Converting 10 g o f steam at 110°C to ice at

-1 0°C a ) 2 4 0 c a l b ) 1 0 .8 k c a l
j c) evaporation of 39 g of Q ,H 6
a)2000 cal b)54000 cat c)3655 cal 5.28 If the heat of evaporation for ethyl alcohol,
T'
, 5.27 Calculate the quantity of heat absorbed or re­ C 2H 5OH, is 9200 cal/mol at its normal boiling point,
leased in the following transitions. how many grams of ethyl alcohol could you evaporate
a) W arming 12 g of water from 25°C to 45°C. \b y condensing 25 liters of steam at 100°C (P= 1 atm)
to liquid water at 0°C? - 47 g
b) Converting 15g ice from 0°C to steam at 100°C.
c) Heating 150 mL alcohol from -110°C to 78°C
5.29 Liquid nitrogen is a very useful refrigerant for
and evaporating the alcohol at 78bC. The melting and
low-temperature experiments. Its normal boiling point
 Condensed Phases o f M atter Liquids and Solids 177

is -195.8°C; its heat o f vaporization is 1330 cal/mol. 5.35

How many calories are needed to vaporize 14g of ni­
trogen at its normal boiling point, how many grams
of water supply this heat when it freezes ?
665cal, 8.3g

5.30 When 30 g o f water vapor at 160°C are sent

onto some ice at 0°C the last situation is found to be
liquid water at 100°C. W hat whs the mass o f ice ?
95 g

5.31 W hen 100 g of a substance at 60°C are placed

on a block o f ice at-20°C, the final tem perature is
measured as 10°C. How many grams o f ice melted ? The temperature dependence of 20 g o f substance
^su b stan ce = 0 .2 C al/g С Ю g on the amount of heat added to the substance is given
* in the graph.
5.32 Equal amounts of ice at-10°C and water at a) W hat are the physical states of substance in the
90°C are mixed.W hat will be the final temperature and regions represented by I, II, III, IV and V ?
the state ? 2 .5 ° C liq.
b) W hat are the melting and boiling temperatures
of the substance ?
5.33 200 g o f ice at-20°C and 100 g of vapor at
c) W hat are the latent heat of fusion and latent heat
105°C are placed into the same container. W hat will
o f vaporization in calories of the substance ?
be the temperature and the state of the mixture?
d) W hat are the specific heats o f solid and liquid
at 100°C 30.1 g vapor
states of the substance ?
*5.34 200 g o f an aluminum block at 400°C is
e) W hat would be the shape o f the curve if 40 g of
placed into a 500 g m ixture o f ice and water. If the
the same substance were heated by the same heater ?
equilibrium temperature o f the system is 40°C, calcu­
late thp mass of ice in the original ice-water mixture. c)Lj-30cal/g, L v= l 3 2 .5 c a ll g

c A i = 0 .2 cal/g°C. 200 g d) с s = 0 , 6 c a l l g °C, C [ = 0 .8 с a l l g ° ( t

V apor Pressure - Boiling Point

5.36 uids?
b) The atmospheric pressure at the top of Erciyes
Mountain is about 700 mmHg. W hat are the boiling
points of these liquids at the top o f Erciyes Mountain?
c) U nder what pressure w ill acetic acid boil at
80°C?

5.37 The boiling points of some liquids are giv­

en:
compound C 2 H5OH H20 C 2 H4 (OH ) 2 C 4 H 1 0 O CH 3 COOII
b.P.(°C) 78.4 too 197 34.5 118
Plots of vapor pressure versus temperature for four
different liquids are shown in figure given above
a) List these liquids in order of increasing intermo-
a) W hat are the normal boiling points o f these liq-
lecular attractive forces.
178 Chapter 5

b) W hich liquid has the low est vapor pressure at 5.39 150 mL of dry helium gas m easured at 80°C
25°C? W hich has the highest ? Explain. and 750 mmHg is bubbled through toluene, C 7H 8 (1),
at 80°C. Assuming that the helium gas is saturated
5.38 A sample o f benzene, СбНб (1), is in dynam­
with toluen vapor at 80°C, what is the volume o f the
ic equilibrium with its vapor at 40°C. A 400 mL of
resulting gaseous mixture if the total pressure remains
the saturated vapor is withdrawn and found to have a
at 750 mmHg and the temperature at 80°C?
mass of 0.32 g. W hat is the vapor pressure o f benzene
P c 7h 8=300 mmHg at 80°C 250 mL
at 40°C. 200 mmHg

P roperties of S olutio ns
5.4Q^fconsider two solutions. One prepared by a) Calculate its molecular weight,
dissolving 1 mol NaCl in 100 g o f H 2O, and the other b) Calculate its empirical formula.
by dissolving 2 mol NaCl in 100 g of H 2O. Compare
cf) Calculate its correct molecular formula.
these two solutions in terms of their a) densities b) va­
a ) 6 2 b) C H 3 Q c) C 2 H 4 ( O H ) 2
por pressures c) boiling points d) freezing points.

5.4;^ Find the freezing and boiling points of the 15.44 Calculate the weight o f m ethanol, CH 3O H ,
solutions prepared by dissolving. (Solutes are nonion­ required to lower the freezing point o f 10.00 liters of
izing in a and b) w ater to -9.3°C. 1600 g

a) 2 mol of glycerol in 1000 g o f water.

b) 5 mol o f urea in 500 g o f water. 5 .45C alculate the freezing point of a water solu­
c) 55.5 g СаС1г in 250 g of water СаС1г (produces tion which is 30% by mass o f ethyl alcohol.
Ca2+ and СГ ions in water). , -1 7.3 °C
a ) f . p = - 3 .7 2 °C b) b .p . = 1 0 5 .1 °C c)f.p.= -11.2°C 5.4(r How many liters o f antifreeze ethylene gly­
col, СгНбОг (d=1.12g/mL) would you add to a car ra­
!5>42)Whcn 92 grams of a compound are dissolved
diator containing 8 liters o f water if the coldest winter
in 2000 gram s o f water, there is a lowering of the
temperature in your area is about -28°C. 6 .6 L
freezing point to -1.86°C. W hat is the m olecular
weight of the compound ? 46 g 5.47 A solution prepared by dissolving 36.8 g of
a nonionizing liquid in 80 g o f w ater boils at
j^ J ig iw h e n 124 grams of alcohol (ethylene gly­ 102.55°C. If the liquid consists of 39.1 % C, 8.7 %
col) are dissolved in 1000 grams of water, the freezing H, and 52.2 % O, what is the molecular formula o f the
point is -3.72°C. Upon analysis it is found to contain liquid?
38.7 % C, 9.7 % H, and 51.6% O. C 3H 8 O3

P e rc e n ta g e C o n c e n tra tio n
5.48 Calculate the percent by mass of the solute 5.49 Calculate the mass of solute present in each
in each of the following solutions. of the following solutions.
a) 15 g NaCl in 360 g water. a).1600 g o f 10 % NaOH solution.
b) 40 g sugar in 762 mL o f solution with a density b) 400 mL of 20% № гС О з solution (d=1.2 g/mL)
of 1.05 g/mL. c) A 40 % alcohol solution prepared by dissolving
c) 200 mL o f glycol (d = l.l g/mL) in 250 grams of enough alcohol in 360 g of water.
solution. a)160g b)96g c)240g
d) 2 mol of C 2H 5OH in 6 mol of H 20 . 5.50 How many liters o f HC1 gas at STP are
needed to prepare 36.5% by mass o f 200 g HC1 solu­
a)4% b)5% c) 8 8 % d)46%
tion ? 44. 8 L

О
Q
±£ 1
 Condensed Phases o f M atter Liquids and Solids 179

5.51 50 g o f the crystal hydrate P e S 0 4.7H20 b) A solution obtained by mixing 200 g o f 10 %

were dissolved in 250 g of water. Calculate the per­ NaCl, 100 g of 20 % NaCl, 40 g of pure NaCl, and 60
centage concentration of the crystal hydrate and the an­ g of water.
hydrous iron(II) sulfate in the solution. c) A solution obtained by mixing 80 g of 15 %
16.7% and 9.1% sugar, 180 g of 40 % sugar solutions and evaporating
10 g of water from the resulting solution.
5.52 The density of pure acetic acid is 1.049
a)22% b)20% c)33.6%
g/mL and the density of a solution prepared by dilut­
ing 333 g of acetic acid to 1 liter is 1.026 g/mL.
a) W hat is the volume percentage of acetic acid in the 5.57 How many grams of water must be evaporat­
solution ? b) Calculate the weight percentage of acetic ed from 200 g o f 30% K N 0 3 solution to make its
acid, C H 3 COOH. 31.7% and 32.4% percentage concentration equal to 50 % ? 80 g

5.53 A solution o f alcohol, C 2H 5OH, at 4°C is 5.58 W hat volume of water must be added to 200
prepared by adding enough water to 31.73 g of alcohol mL of a 30% solution of NaOH (d=1.33 g/mL) to ob­
to make a total volume of 100 mL. The density of tain a 10% solution of NaOH ? 53 2 mL
pure alcohol at 4°C is 0.7932 g/mL and that of the so­
lution is 0.9510 g/mL. 5.59 How many moles of M gS 0 4 .7 H 20 must be
a) W hat is the volume percentage of alcohol in the added to 100 mol of H 2O to obtain a 10 % M gS 04 so­
solution? lution by mass. 1.89 mol

b) W hat is the weight percentage of alcohol?

5.60 How many moles of KOH are contained in
40% and 33.36%
400 mL of 28 % KOH solution that has a density of
1.25 g/mL. KOH=56 2.5 mol
5.54 Calculate the new percentage by mass of
NaCl after each of the following is added to 360 g of
5.61 To prepare 100 mL o f 16.4 % H 2SO 4 solu­
20 % salt solution.
tion (d = l.l g/mL), what volumes of water and 98 %
a) 40 g of water b) 40 g of salt
H 2SO 4 solution (d=1.84 g/mL) must be mixed ?
c) 40 g of salt and 100 g of water.
1 0 m L 9 8 % H 2 S 0 4 , 90 m L H 2 0
a)1 8% b)28% c)22.4%

5.55 Consider 250 g of 40 % H2SO 4 solution. 5.62 1 liter o f a solution has 5 mol o f X. If it is
a) How many grams of water must be added to this 20 % X by mass and has a density o f 1.4 g/mL, what
solution to make its percentage concentration 25 %? is the molecular weight of X? 56 g/mol
b) How many grams of water m ust be evaporated
from the solution to make its percentage concentration 5.63 0.4 mol of XBr 2 required to prepare 200 g of
50 %? . a)1 5 0 g b)50g 40 % ХВГ2 solution by mass. W hat is the atom ic
weight of X ? Br=80
5.56 Calculate the percent by mass of the solute 40 g/mol
in each of the following solutions. 5.64 One m illiliter o f a 25% solution contains
a) A solution obtained by mixing 300 g of 20 %0.458 g of the solute. W hat is the density of the solu­
KC1 and 200 g of 25 % KC1 solutions. tion ? 1. 83 g / m L
180 Chapter 5

M o lar C o n c e n tra tio n

5.65 Calculate the molarity of each of the follow­ a) A 36,5 % HC1 solution with d= 1.18 g/mL.
ing solutions. b) A 98 % H 2S 0 4 solution with d=1.84 g/mL.
a) 0.25 mol o f NaOH in 500 mL of solution. c) A 80 % С 2Н 5<ЭН solution with d=0.92 g/mL.
b) 126 g o f HNO 3 in 5 L o f solution. d) A 50.4 % HNO 3 solution with d=1.3 g/mL.
c) 1.2xl0 24 H 2SO 4 molecules in 400 mL of solu­ e) A 6 % CH 3COOH solution with d=1.05 g/mL.
tion. a)11.8 b)18.4 c)16 d)10.4 e)1.05
d) 5.6 L o f NH 3 measured at 0°C and 2 atm in 2 L
of solution. a)0.5 b)0.4 c)5 d)0.25 5.70 Describe how would you prepare 500 mL of
0.1M CaBr 2 solution from each of the following.
5.66 Calculate the num ber of moles and grams of a) Solid 100 % pure CaBr 2 b) CaBr 2.2H20
solute necessary to prepare each of the following solu­ c) A 80 % pure CaBr 2 sample
tions d) 100 mL of 0.5M CaBr 2
a) 2 L of 0.25M NaOH. e) 1000 mL 0.05M CaBr 2
b) 300 mL o f 0.2M N a N 0 3. d)Add 400 mL of water to the solution
c) 200 mL o f 1M C a S 0 4.2H 20 . e)evaporate 500 mL of water
a)0.5mol, 20g b)5.1g c)34.4g 5.71 To prepare 400 mL of 2 M H 2S 0 4 solution,
5.67 Calculate the volume o f 0.2 M solution that 100 mL of H 2S 0 4 solution whose density is 1.4g/mL
can be prepared with each of the following. are used. W hat is the percentage concentration of the
a) 25 millimole o f KNO 3 given solution. 56%
b) 40 g of CaBr 2
c) 8.96 L of HC1 at STP. 5.72 17.1 g o f X 2(S 0 4)3 is required to prepare 400
d) 100 mL of 0.5M NaCl mL of 0.125 M solution. W hat is the atomic weight
e) 5 g impure sample containing 80 % NaOH by of X ? S=32, 0 = 1 6 27 g/mol
mass. a) 1 25 m L b ) l L c)2L e)0.5L
5.73 600 mL o f 0.5M X(OH )2 solution is pre­
5.68 Calculate pared from 255 g X(OH )2 solution that contains 20 %
k ) the mass o f 40 % CaBr 2 solution necessary to X(OH )2 by mass. Find the atomic weight o f X. 0= 1 6,
prepare 600 mL o f 0.5M CaBr2. H=1 136 g/mol
b) the mass o f 75 % N aOH solution necessary to
prepare 400 mL o f 1.5M NaOH solution *5.74 When calcium metal is added to water, cal­
c) the volume o f HBr (g) measured at 27°C and cium hydroxide and hydrogen gas arc produced. When
684 torr necessary to prepare 300 mL of 4 M HBr. a quantity of calcium is reacted with water, 4.48 L of
c)150 b)32 c)32.8L H 2 at STP is produced. If the final volume of the re­
5.69 Calculate the molarity of each of the follow­ sulting solution is 200 mL, what is the molarity of
ing solutions whose percentage composition by mass calcium hydroxide in the solution ?
and densities are given. 1M
L
Dilution and M ixing S olutio ns

5.75 Calculate the m olarity o f the solution pre­ 5.76 Consider 800 mL of 0.4M H 2S 0 4. a) W hat
pared by mixing a) 150 mL of 0.6M AgN 03 with volume of water must be evaporated from the solution
350 mL of H20 b) 100 mL o f 6 M NaOH with 400 in order to increase the concentration o f the solution to
mL of 2M NaOH c) 200 mL o f 36.5 % HC1 solution 0.5M ? b) W hat volume of water must be added to the
(d=1.2 g/mL) with 800 mL o f 7.3 % HC1 solution solution to decrease its concentration to 0.25M ?
.(d = l.l g/mL) a) 0. 18 b ) 2 .8 c ) 4 . 1 6 a)160 mL b)480 _ mL
 Condensed Phases o f M atter Liijuids and Solids 181

5.77 How many mL of 98% H 2S 0 4 by mass so­ H 2S 0 4 have to be mixed to prepare 120 mL of a 1M
lution with a density of 1.84 g/mL are needed to pre­ solution? «. " 96mL and 24mL
gg.
pare 100 mL of 0.1M H 2S 0 4 solution?
0.543 mt 5.82 W hat volum es of 2M and 4M СаС1г solu­
5.78 W hat volum es of 8 M NaNC>3 and w ater tions have to be mixed to give 6 L o f 2.5M CaClj so­
must be added to 2 L o f 2M NaNC>3 solution in order lution.? 4. 5 L a n d 1. 5 L

to obtain a 8 L o f 5M ЫаИОз solution. •'*

4.5 L a n d 1. 5 L 5.83 In what volume ratios should the following
5/79 11.4 g of solid MgCl 2 and 400 mL o f water pair of solutions be mixed to obtain a 2M solution?
are added to 600 mL o f 0.8 M M gCl 2. W hat is the a) 1.2M KC1 and 3.6 M KC1.
molarity of the resulting solution ? M gCl 2=95 (Ne­ b) 0.75 M K M n 0 4 and 2.25M K M n 0 4
glect volume change) 0 .6 M c) 0.5 M H N 0 3 and 11M HNO 3
a)2/l b)l/5 c)6/l

5.80 How many mL of w ater m ust be added to 5.84 The acid solution in a fully charged battery is
100 mL o f 6 M H 2S0 4 solution so that the concentra­ 33 % H 25>0 4'by mass and has a density o f 1.25 g/mL.
tion of the resulting solution will be 2M? 2 0 0 mL a) W hat is its molarity ? b) How many mL o f 18.4 M
ft H 2S 0 4 solution are needed to fill a 3 L lead storage
5.81 W hat volumes of 0.5M and 3M solutions of battery ? 4.2M, 685mL

C hem ical R eactio ns in S olutio ns

5.85 Consider<he reaction*: *If 4.35 g XO 2 reacts com pletely with 400 mL of
2HN03 (aq) + Ba(OH)2(aq) Ba(N 03 ) 2(aq) + 2H 20(1) 0.5 M HCI solution, calculate
If 10 mL o f Ba(OH )2 solution completely reacts with a) the atomic weight of the element X. *
40 mL o f 0.1 M HNO 3 , what is the m olarity of b) the volume of CI2 gas measured at 2 atm and
B a (O H )2 solution ? 0 . 2 M . 37°C . 0 = 1 6 a )5 5 g /m o l b)635.5m L

5.86 Given the reaction : 5.90 2.88 g o f Х 4С з reacts com pletely with
СаС О з **" 2 H N O 3 —> C a (N 0 3)2 + H 20 + C 0 2 / 600 mL of 0.4 M HCI according to the equation:
X 4C 3 (s) + 12HC1 (aq) -> 4XC13 (aq) + 3CH 4 (g)
If 20 mL H N O 3 solution reacts exactly with 0.250 g
Calculate the atomic weight of X. C=12 27 g/mol
of C a C 0 3, what is the molarity of the acid ? 0. 25 M
ь

5.87 W hat volume of H 2S (g) at STP is required 5.91 2 K M n 0 4 (aq) + 16HC1 (aq) ->
to react completely with 200 п ф o f 0.2M РЬ(Ж>з )2 2M nCl2 (aq) + 2KC1 (aq) + 8H20 (1) + 5C12 (g)
solution ? A sample o f 150 g o f K M n 0 4 sample that is 79 %
P b (N 0 3)2 (aq) + H2S (g) -4 PbS (s) + 2 H N 0 3 (aq) K M n 0 4 is allowed to react with 400 mL of a HCI so­
896 mL lution having a density o f 1*.2 g/mL and containing
5.88 W hen a 25 g impure sample o f Cu is reacted 36.5 % HCI by mass. How many liters of CI2 (g) at
com pletely with 400 mL of H NO 3 solution, 3 L of STP is produced by the reaction ? 33.6 L
NO (g) measured at 27°C and 1.64 atm is produced ac­
cording to the reaction. 5.92 An alloy o f Cu and Ag is known to contain
3Cu + 8HNO 3 -> 3 C u (N 0 3)2 + 2NO + 4H20 64 % Cu and 36 % Ag by mass. How many mL o f
a) W hat is the molarity of HNO 3 solution ? 4M HNO 3 are required to dissolve 30 g of this alloy?
b) W hat is the percentage purity of copper sample? Cu=64, Ag=108
a)2M b)76.8% Cu + 4 H N 0 3 -> C u (N 0 3)2 + 2 N 0 2 + 2H20
5.89 Consider the equation : Ag + 2 HNO 3 —> AgNC>3 + NO 2 + H 2O
X 0 2 + 4HC1 -> XC12 + 2H20 + Cl2 350 mL
 V

182 Chapter 5

N o r m a lit y
5.93 C alculate the norm ality of each o f the fol­ b) 500 mL of 0.4 N Na 2C 0 3
lowing solutions. c) 1200 mL of 2 N Sr(OH )2
a) 70 g of NaOH in 500 mL of solution. a)63 b)10.6 c)146.4 g
b) 24.5 g of H 2SO 4 in 200 mL of solution. 5.95 Calculate the volume of 0.1 N CUSO 4 solu­
c) 21.2 g of K 3PO 4 in 1200 mL o f solution. tion that would contain 8 g o f CUSO 4 . 1L
a)3.5 b)2.5 c)0.25
5.94 How many grams of solute are contained in 5.96 Calculate the volume of 0.5 N AICI3 solu­
each of the following solutions ? tion that could be prepared from 100 mL of 1M AICI3
a) 2 L of 0.5 N HNO 3 solution. 600 mL

S o lu b ilit y
5.97 W hen 20 g of NaCl is placccfin 60 g of wa­ is increased to 70°C. How many grams o f salt must be
ter, 2 g of NaCl remains undissolved. W hat is the sol­ added to saturate the solution? If this saturated solution
ubility o f NaCl in g/100 g H20 at this temperature ? at 70°C is cooled to 30°C, how many grams o f salt
3 0 g / 1 0 0 g H 20 will crystallize? What is the percentage of the saturated
solution at 30°C ? 2 0 0 g, 2 0 0 g, 2 8 . 6 %
5.98 The solubility o f A g N 0 3 is 220 g/100 g
H 20 at 20°C. How many grams o f water are needed to
5.103 The solubility o f carbon dioxide in water
dissolve 55 g of A g N 0 3 at the same temperature?
is 335 mg per 100 g water at 0°C when the partial
25 g
pressure o f C 0 2 is 760 torr. How many mg o f C 0 2
5.99 Solubility of a solid X is 30 g/100 g H 20 at will dissolve in 1 kg of water at 0°C when the partial
25-°C. How many grams of X must be added to satu­ pressure of CO 2 is 5 atm? 16750 mg
rate a solution which was prepared with 50 g o f X and
3 0 0 g o f H 20 at 2 5 °C ? 40 g 5.104

5 .1 0 0 W hen 300 g o f a 15% solution were

cooled, part of the solute precipitated and the concen­
tration of the solution becam e equal to 8 %. W hat is
the mass of the precipitate? 2 2 .8 g

5.101 The solubility of copper sulfate at 30°C is Temperature (°C)

25 g per 100 g of H 20 . W ill an 18 % solution of the Answer the following questions by using the graph
salt be saturated at this temperature ? No which shows the temperature dependence of solubility
of two solids.
5.102 Solubility o f a salt is 140 g/100 g H 20 at a) W hat is the maximum grams of KNO 3 that can
70°C and is 40 g/100 g H 20 at 30°C. 80 g of salt is be dissolved in 400 g of water at 50°C ?
placed into 200 mL of water and then the temperature b) A solution is prepared by dissolving 60 g of

\
 Condensed Phases o f Matter Liquids and Solids 183

KNO 3 in 250 g o f water at 20°C. How many grams of c) When a quantity of saturated solution of KNO 3
K N O 3 m ust be dissolved to saturate this solution at at 60°C is cooled to 20°C, 120 g o f solid KNO 3 pre­
20°C ? cipitated. W hat is the mass of water used in the prepar­
c) At 30°C, a saturated solution of К 2СГ2О 7 in ation of the solution ?
300 g H 2O is prepared, and then it is heated to 50°C. a)340g b)15g c)45g d)80 e)150
How much more К 2СГ2О 7 can be dissolved in this so­ 5.105 The solubility of X is 30 g X/100 g H 2O
lution at 50°C ? at 20°C. A solution is prepared by dissolving 0.4 mol
d) A 520 g o f saturated solution o f К 2СГ2О 7 at of X in 300 g of H 2O. Later it was determined that the
50°C is cooled to 10°C. How many grams o f solute solution could dissolve 40 g of X more. Calculate the
will crystallize from the solution ? molecular weight of X. 125 g/ mo l

Ion C o n c e n tra tio n

5.106 W rite the dissolving reaction of each of the 5.111 W hat are the concentrations o f Na+, M g2+,
following ionic substances in water. A l3+, CF if 300 mL of 0.2 M NaCl, 400 ml of 0.3 M
a) A g N 0 3 b) CaCl 2 c) A12( S 0 4)3 d) FeCl 3 M gC l 2 and 300 mL o f 0.2 M A1C13 solutions are
W hat are the concentration of ions in 1 M solution mixed ?
of each solute ? [ N a +]=0.06M [ M g 2 +]= 0 . 1 2 M [ M 3+J= 0 .0 6 M
[ С Г ]=0.48 M
5.107 A solution is prepared by dissolving
17.1 g of A12( S 0 4)3 in sufficient water to make 500
5.112 300 mL of 0.5 M XC12 and 500 mL o f
mL of solution. W hat are the concentrations of Al3+
0.2 M YCln solutions are mixed. If the СГ ion con­
and S 0 4" ions in the solution ? A l2(S04)3=342
centration in the final solution is 0.75 M, what is the
0.2M and 0.3M
value of n ? • 3
5.108 4.84 g o f F e (N 0 3)3 is used to prepare a
certain volume of solution in which the molar concen­ 5.113 W hen a 8.22 g m ixture o f C aC l 2 and
tration of N 0 3 ion is 0.12 M. W hat is the volume of AICI3 is dissolved in sufficient water to make 400 mL
the solution ? F e (N 0 3)3=242 500 mL of solution, the СГ concentration in the solution is
found to be 0.4 M. W hat is the mass o f AICI3 in the
5.109 2.78 g o f F e S 0 4.xH 20 is used to prepare
'I original mixture? 2.67 g
500 mL of a solution in which the molarity of S 0 4"
is found to be 0.02- M. W hat is the value o f x ? 7
5.114 W hat volumes of 0.3 M F e (N 0 3)2 and
0.2 M A g N 0 3 solutions must be mixed to prepare a
5.110 W hat arc the concentrations o f C a 2+,H+,
800 mL solution with a NO 3 ion concentration of 0.5
Cl" in a solution if 500 mL of the solution is pre­
M? 600 mL a n d 200 mL
pared from 0.2 mol CaCl 2.2 H 20 and 0.15 mol HCI?
Both C aC l 2 and HCI are fully dissociated into ions in 5.115 7.52 g X ( N 0 3 ) 2 is used to prepare a 250
aqueous solution. mL solution in which the NO 3 ion concentration is
[C a + 2]=0.4M [СГ]=1.1М [ H + J= 0 . 3 M 0.32 M. W hat is the atomic weight of X ? 64

P re cip ita tio n R ea c tio ns

5.116 300 mL o f 0.1 M C aC l 2 and 200 mL of b) W hat is the m axim um num ber o f m oles o f
0.4 M AgNC>3 solutions are mixed in order to obtain a AgCI precipitated ?
precipitate of AgCI. c) Calculate the molar concentration o f each ion re-
a) W rite the overall equation, and net ionic equa- maining in the solution at the end of reaction,
tion of the reaction. b ) 0 .0 6 c ) [ C a 2+]^0.06 [ A g + ]=0.04
[ N O ’3 ] = 0 . 1 6 [ С Г ]=negligible
1841 Chapter 5

5.117 When 200 mL of 0.4 М A1(N0 3)3 and 600 the molarity of A g+ is found to be 0.5 M after precipi­
mL of 0.2 M KOH solutiops are mixed, Al(OH )3 pre­ tation, what is the volume of N al solution ? 4 0 m L
V-
cipitates. (a). W rite the com plete and net ionic equa­ 5.122 Gaseous H 2S was passed through 125 mL
tions for the reaction. (b).-How many grams of of a solution containing C u 2+ io n s until all the cop­
A l(O H )3 are fornied ? (c) Calculate the molarity of per had precipitated as CuS. If 4.8 g of CuS was
each ion after the precipitation. formed, what was the molarity of the C u 2+ in the so­
b)3.I2g с) [ Л1 3 + ] = 0 . О5 М lution ? (CuS = 96) ' "
5.118 The addition of excess К 2С Ю 4 solution to * 0.4 M
200 mL of A g N 0 3 solution precipitated 16.6 g of
5.123 Solution A contains [B a2+] = 0.25 M and
Ag 2CrC>4. W hat was the molarity of A g N 0 3 solution?
solution В contains [ S 0 2']= 0.4 M. Assuming that
A g 2C r 0 4=332 0.5 M
1 * B aS 0 4 has a negligible solubility in water, calculate
«■ w hat happens w hen-20 mL o f solution A is mixed
5.119 Excess silver nitrate solution is added to
with 10 mL of solution B, what remains in the solu­
50 mL o f 0.1 M HC1 solution. W hat weight of insol­
tion? 0.004 m ol B a S O 4 p p t a n d 0.001 m o l
uble AgCl will precipitate? 0. 72 g и 2 + r e m a i•n s .
Ba
**5.124 A one liter solution contains Fe3+ and
5.120 W hat volum e of 0.5 M N aO H solution
Mg2+ ions. The addition of 1 L of 1.2 M NaOH is just
must be added to 60 mL of 1 M Al2(S 04)3 so that all
required to precipitate these iorts as Fe(OH )3 and
the Al3+ ions are precipitated as Al(OH)3. 720 mL
M g(O H ) 2- The total mass o f the precipitate is 38.8 g.
W hat is the Fc3+ ion concentration in the original so­
5 .1 2 1 A 200 mL o f 1 M A g N 0 3 solution is
lution ? Mg=24, Fe=56 0.2M
mixed with a 2 M N al solution and Agl precipitates.If

SELF TEST

W hich of the follow ing substances has the pure water salty water water-t- alcohol
highest boiling point under the indicated pressure. ? A) I II III
Substance Pressure (torr) B) I III II
A) pure water 760 C) III I II
B) pure water 700 D) III II . I
C) 0.1 M sugar solution 760 E) II Ill , I
D) 0.1 M NaCl solution 700
3.
1200
900
1. A student is given three transparent liquids,
I о 600
pure water, salty water and a mixture of water and al­
cohol. He heated the liquids, recorded their temperature 300
changes, and finally plotted the following graphs.
4 0 90 T em p (°C)
The graph shows the heating curve of a solid from
0°C to 90°C. If the latent heat of fusion of the solid is
60 cal/g, which is the specific heat o f liquid state of
this substance in cal/g°C ?
A) 0.60 B) 0.50 C) 0 .7 5 \V D) 0.80 E) 1.0
h e a tin g tim e 4. If 20 g of ice at -10°C and 20 g o f w ater at
80°C are mixed, which will be the final state and the
W hich o f these graphs belongs to which sub­ temperature of the mixture ?
stance? A) Water .over zero degree B) Water at zero degree
 I
Condensed Phases o f Matter Liquids and Solids 185

C) Ice-Water at zero degree D) Ice at zero degree 12. A 50 g impure sample o f A1(N0 3)3 is dis­
E) Ice below zero degree solved in sufficient water to make 400 mL of solution.
If the [N 0 3 ] in the solution is 1.5 M , which is the
$^W hat mass of a 20% solution of KOH must be percentage of A1(N0 3)3 in the sample?MW=213 g/mol
added to 1 kg of a 50% solution to obtain a 25% solu­ A) 28.4 B) 42.6 C) 56.8 D) 85.2 E) 99.4
tion ? 13. W hen 20 g o f C aX 2 is used to prepare
A) 6 kg B) 5 kg C) 4 kg D) 2.5 kg E) 1 kg 200mL of a solution, the molarity of X ' is found to be
1 M. W hat is the atomic weight of X ? (Ca = 40)
6 . The solubility o f X at 50°C is 0.125 mol
A) 20 B) 35 C) 80 D) 160 E) 200
X/100 g o f water. If the saturated solution of X at
50°C is 20% X by mass, which is the m olecular 14. Equal volumes of 1 M K N 0 3, 4 M Pb(N 03)2
weight of X? and 6 M Fe(N 03)3 solutions are mixed. W hat is the
A) 125 g/mol B) 160 g/mol C) 200 g/mol molar concentration of N 0 3 ion in the resulting solu­
D) 250 g/mol E) 400 g/mol tion?
A) 9 M В) 6 M C) 4 M D) 3 M E) 2 M
7. The solubility of potassium chlorate at 70°C is
30 g, and at 30°C, 10 g in 100 g o f water. How many 15. How many Al3+ ions are there in 10 mL of
grams of potassium chlorate will precipitate from 65 g 3 N AlBr3.6H20 (MW=375) ?
of a solution saturated at 70°C if it is cooled to 30°C? A) 3 x l0 21 B ) 6 x l0 21 C ) 5 x l0 22
A) 5 B) 10 C) 15 D) 20 E) 30 D) 9 x l0 22 E) 6 x l0 23

$Гб.84 g of A 12(S 0 4)3 is used to prepare 400 mL 16. How many liters o f C 0 2 measured at STP,
of solution. Which one of the following statements is would be produced by the action of 200 m L .of 2 M
WRONG for this solution ? A12(S 0 4)3=342 g/mol HCI on C a C 0 3 ?
A) The solution contains 0.02 mol o f solute. C aC 0 3(s)+ 2HCl(aq) -> C aCl 2(aq) + C 0 2(g) +H 20(1)
B) [Al3+] = 0.1 M in the solution. A) 2.24 Cl) 4.48 C) 6.72 D) 8.96 E) 17.92
C) [SO2- ] = 0.15 M in the solution. 17. Consider the reaction :
D) If 600 mL of water is added to the solution the H 2S 0 4(aq) + 2KOH(aq) K2S 0 4(aq) + 2H 20(1)
[SO2' ] becomes 0.06 M. How many mL o f 0.08 M KOH solution will
E) When the volume of the solution is decreased to completely react with 25 mL of 0.2 M H 2S 0 4 ?
200 mL by evaporating water [Al3+] becomes 0.15 M. A) 250 B) 125 C) 100 D) 75 E) 25

9.8.2 L of HCI (g) measured at 0.75 atm and 27°C 18. How many moles o f H 2 would be produced by
is used to prepare a 2.5 L HCI solution. W hat is the the action o f 30 mL o f 2 M HCI on 5.4 g of Al?
molarity of HCI in the solution? A1=27 2A1 (s) + 6HC1 (aq) -> 2A1C13 (aq) + 3H 2 (g)
A) 0.05 B )0 .1 0 C) 0.15 D) 0.20 E) 0.25 A) 0.01 B) 0.02 C) 0.03 D) 0.04 E) 0.05

10.To what volume would 10 mL of 2 M Na 2S 0 4 19. The addition of excess BaCl 2 solution to 200
solution have to be diluted in order that the resulting mL of N a 3P 0 4 solution precipitated 180.3 g of
solution will contain 9.2 mg of Na+ ion per milliliter? Ba 3(P 0 4)2 (MW=601 g/mol). Which was the molarity
Na=23 of Na 3P 0 4 solution ?
A) 20 B) 40 C) 60 D) 80 E) 100 A) 1 * B) 2 ' C) 3 D) 4 E) 5
20.W hen 200 mL o f 0.2M P b (N 0 3) 2 solution is
11. A 100 mL оГ 10 % NH 3 solution that has a mixed with 300 mL of 0.3 M NaCl solution, P bC l 2
density o f 0.85 g/mL is diluted to 1000 mL. Which is precipitates. Which is the molarity of С Г after precipi­
the molarity of NH 3 in the resulting solulion?NH3=17 tation stops ?
A) 5 ^ B) 2.5 C) 1.5 D) 1 E) 0.5
A) 0.18 B) 0.10 C) 0.08 D) 0.04 E) 0.02
 и

CHAPTER

Atomic Structure and

Chemical Periodicity
__________; Г \

The objectives of this chapter are to enable the student to :

1. Recognize the significance of chemical laws as chemical
evidences for atoms.
2. Recognize Faraday's Laws for the electrical nature of
m a tte r.
3. List the subatomic particles and describe their proper­
tie s .
4. Describe Thomson's atomic model.
5. Decribe Rutherford's experiment and explain the conclu­
s io n .
6. Define isotopes and give examples.
7. Describe the Bohr atom, and explain its relationship with
the spectrum of hydrogen atom.
9. Describe quantum numbers on the basis of wave mechan­
ics.
9. Write the electronic configurations.
11. Recognize the significance of groups and periods in the
periodic table.
12. Recognize the relationship between atomic structure and
atom ic size, ionization energy, oxidation numbers, and electro­
n e g a tiv ity .
 Atomic Structure and Chemical Periodicity 189

S u p p o se th a t you h av e a p iece o f p a p e r and a p a ir o f sc isso rs, h o w far

can you g o cu tting the p a p e r in h alf, then cu ttin g the h alv e s in h a lf again and
ag ain ? O b v io u sly , ev en a fter n u m e ro u s d iv isio n s the size o f the p a p e r n e v e r
beco m es zero, b u t this continual su b division w ill lead to a p article th at can n o t
be d iv id ed further. M any p h ilo sophers reasoned in the sam e w ay you did, and
expressed that all the m atter w as com posed o f tiny, indivisible particles, called
atom s. H o w ever, a series o f discoveries in the la te r part o f the n in eteen th c e n ­
tury has show n th at atom s are m ore com plex th an philosophers had im agined.
In th is c h a p te r w e w ill ex a m in e som e o f ch em ical ev id en ces th at lead
scientists to the atom ic theory o f m atter, and the evolution o f atom ic theory.

6.1 CHEMICAL EVIDENCES FOR ATOMS

T h e d ev elopm ent o f the atom ic theory involved co n tributions from m any
scien tists. J o h n D a lto n (1 7 7 6 -1 8 4 4 ) w as th e first c h e m ist w h o se c o n trib u ­
tio n w as u n iq ue. H e based h is assu m p tio n s on q u a n titativ e data. D alto n d e ­
rived the q u an titative aspects o f his theory from the law s o f chem ical ch ange :
the law o f con servation o f m ass, the law o f definite p ro p o rtio n s a n d the la w o f
m u ltip le p ro p o rtio n s. G ay-L u ssa c's L a w o f co m b in in g volum es and F ara d a y's
L a w s o f electrolysis also serve for the d evelopm ent o f atom ic theory.
T h e p r i n c ip a l p o s tu la te s o f D a lto n 's th e o r y a r e :
1. A ll m a tter is o f extrem ely sm a ll indestructible, p a rtic le s ca lled atom s.
A n a to m is th e sm a llest p a rtic le o f an elem ent. A ll a to m s o f the sa m e e lem e n t
a re iden tica l in m ass (a n d in other p ro p erties) a n d a tom s o f d ifferen t elem ents
are different.
2. A ch em ica l c o m p o u n d is the resu lt o f the com b in a tio n o f a to m s o f tw o
o r m ore elem ents in a num erical ratio.
3. A to m s can be neither created nor destro yed during a ch em ical change.
N o atom o f o n e elem ent is converted into an atom o f an o th er elem ent.
A series o f recen t e x p erim en t revealed th at atom s are m ad e up o f even
sm aller p articles (subatom ic particles). N ev erth eless, D alton's theory is one o f
the cornerstones o f the m o d em chem istry.

6.1.1 LAW OF D E F IN IT E P R O P O R T IO N S
In a g iven ch em ica l com pound, the elem ents are alw ays c o m b in ed in the
sa m e p ro p o rtio n by m ass.
Since a giv en com pound is the result o f the com b in atio n o f atom s o f tw o
o r m o re e le m e n ts in a fix ed ratio, the p ro p o rtio n s by m ass o f the elem en ts
p resen t in the com pound are also fixed. Jo seph P ro u st (1754-1826) p erform ed
a g reat n u m b e r o f analyses to show the constancy o f co m p o sitio n o f chem ical
c o m p o u n d s. H e found th a t the p e rc e n ta g e c o m p o sitio n o f a c o m p o u n d by
m a ss is a lw a y s constant. F o r ex am p le, if w a te r is fo rm ed from a m ix tu re o f
h y d ro g en and o x y g en g ases, it w ill alw ays co n tain 2 g o f hy d ro g en fo r every
16 g o f oxygen.
190 Chapter 6

H 2 (g) + 1 /2 0 2 (g) -ч > H20 (1)

2g 16 g 18 g
T h e ra tio o f h y d ro g e n to o x y g e n is 2 /1 6 = 1/8. T h e am o u n t o f w a te r
sam p le d o e sn 't m atte r fo r o u r p u rp o ses. A 36 g sam ple o f w a te r c o n ta in s 4 g
o f h y d ro g en co m b in ed w ith 32 g o f o x ygen. T h e ratio o f 4 g o f h y d ro g en to
32 g o f o x y g en is l / 8 .T his ratio is alw ays the sam e fo r w ate r no m a tte r h o w it
is p repared.

EXAMPLE 6 .1 R ecogn izin g L aw of Definite Prop ortion s

Problem : In one experim ent 2.0 g of sodium metal was allowed to react with 20.0 g of chlorine gas. The
sodium was completely used up and 5.08 g of sodium chloride (NaCl) was produced. In a second experiment 2.0
g of chlorine was allowed to react with 20.0 g o f sodium. The chlorine was used up completely and 3.3 g o f so­
dium chloride was produced. Show that these results are consistent with the law of definite proportions.
Solution : From the first experim ent we see that 2.0 g of sodium reacts with. (5.08 - 2.0) or 3.08 g o f chlo­
rine. The ratio o f Na to C l 2 is 2 .0 / 3 .0 8 = 0 .6 5
The second experim ent tells us 2.0 g o f Cl 2 reacts with (3.3 - 2.0) or 1.3 g of Na.
Then the ratio is 1.3/2.0 = 0.65. W e see that elements combine in the same ratio by mass to give a specific
compound.

EXAMPLE 6.2 R e c o g n iz in g L a w o f D e fin ite P r o p o r tio n s .

Problem : The ratio o f A to В by mass in a compound of A and В elements is 6/15. W hat is the maximum
grams of compound resulted by the reaction o f 20 g of A with 45 g of В ?
* , л. m A _ 20 _ 6.67
Solution : First let us check if the ratio o f masses of elements is inproper ratio. ~
Since the ratio is greater than the combining ratio (6/15) of the elements in the given compound, then some of
the A cannot combine with B.
If 6 g A combines with 15 g В 1
„ f x = 18 g o f A
x g A 45 g В J
45 g o f В can combine with 18 g of A to give (45+18) or 63 g of compound and (20-18) or 2 g o f A remains ex­
cess.

EXER C ISE 6.1 In a compound the ratio of A to В by mass is 2/5. If 20 g of each clement arc reacted to
give a reaction, how many grams of the compound can be obtained at most ? 28 g

EXERCISE 6.2 One fifth of a compound containing X and Y is X. When 20 g of a mixture o f X and Y
are reacted, 5 g of X remain unreactcd. What is the weight o f X in the mixture ? 8 g

EXAMPLE 6.3 R e c o g n iz in g L aw of D e fin ite P r o p o r tio n s

Problem : In the com pound X 2Y 3 the ratio of X to Y by mass is 9 / 10. If the atomic weight of X is 27,
what is the atomic weight o f Y ?
Solution : The ratio tells us that 9 g o f X com bine with 10 g of Y. In the compound X 2Y 3,2 mol o f X
combine with 3 mol o f Y. 2 mol o f X weigh 2 x 27 = 54 g, and then,
 Atomic Structure and Chemical Periodicity 191

if 9 g of X combine with lO g o fY 1
1 x = 60 g o f Y.
54 g o f X combine with______ x *
60 g is ihe weight o f 3 mol o f Y. n = m / AW => AW = 60 / 3 = 20 g / mol

E X E R C I S E 6 . 3 The compound CaX 3 is 20 % Cu by mass. What is the atomic weight of X ? Ca=40

80 g/mol

6.1.2 LA W OF M U L T IP L E P R O P O R T IO N S
O ne p o w erful piece o f evid en ce fo r D alto n 's T h eo ry cam e w h en D alto n
and o th e r scien tists studied elem en ts th a t could co m b in e to giv e tw o o r m ore
c o m p o u n d s. W h en ev er tw o elem en ts co m b in e to fo r m m o re th a n o n e co m ­
p o u n d , the d iffe re n t m a sse s o f o n e th a t co m b in e w ith the sa m e m a ss o f the
o th er are in the ratio o f sm all w hole num bers.
F o r ex am p le, carb o n and o x y g en form tw o co m p o u n d s : c arb o n dioxide
and carb o n m onoxide. In carb o n dioxide, tw o atom s o f oxy g en are com bined
w ith o n e atom o f carb o n , and in c arb o n m o n o x id e, one atom o f o x y g e n is
co m b in ed w ith one atom o f carbon.
^ compound m e (g) mo (g) (m o W (m o )c o 2
Carbon monoxide, CO 12 (constant 16
16/32 = 1/2
vCarbon dioxide, C 0 2 12 mass) 32 J
C o n sid er the co m pounds betw een n itro g e n and o x ygen fo r an o th er ex-
mN mo ratio
am p le.T h e ex p erim en ts show th at in o n e o f the co m p o u n d s, 14 g o f n itro ­
C om p I m 16
1 6 / 4 0 = 2 / 5 g en h av e co m bined w ith 16 g o f ox y g en , w hile in an o th er c o m p o u n d , 14 g
C om p 11 ж 40
o f n itro g en h ave com bined w ith 4 0 g o f oxygen. T h e m asses o f oxy g en that
c o m b in e w ith 14 g o f n itro g en are in the ratio o f 16 to 4 0 o r 2 to 5. T hese
n u m b ers are alw ays integers (not fractions) b ecau se atom s can n o t be d iv id ­
ed.
T h e la w o f m u ltip le p ro p o rtio n s show s th at a ch em ical e le m e n t is c o m ­
p o sed o f sm all in d ivisible, in d estru ctib le particles called atom s and all atom s
o f a given elem ent are identical in m ass, (w eight).

EXAMPLE 6 . 4 I llu s tr a tin g th e L aw of M u ltip le P r o p o r tio n s

Problem : Manganese and oxygen give two different compounds, Mn20 3 and Mn30 4. What is the ratio of
oxygen atoms by mass which combine with the same amount o f Mn ? Mn= 55, 0 = 1 6
Solution :
\
^Compound mMn(g) m0 (g)
Мпг0 3 2x55=110 3x16=48
v Mn30 4 3x55=165 4 x l6 = 6 4 y
Now let us equalize the masses o f Mn in both compounds, by multiplying the amounts o f elements by a com
mon factor for each compound
192 Chapter 6

'C o m p o u n d m.Mn (g) m o (g) (т о )м п 20 з ^ т о)м пз 0 4

МП2О 3 3x110=330 3x48=144
144/128 = 9 /8
X МП3 О 4 2x165=330 2x64=128 V J
We see that the ratio of the masses of oxygen atoms combined with a fixed mass of Mn in both compounds is
9/8, a ratio that can be expressed by a small whole numbers.
(b) Instead of weights we can use the number of moles of atoms.
In Mn 20 3 : 2 mol of Mn 3 mol of О =t> 2 x 3 = 6 mol Mn 3 x 3 = 9 mol О r
In Mn 30 4 : 3 mol of Mn 4 mol of О => 3 x 2 = 6 mol Mn 4 x 2 = 8 mol О I *^

6 .4 X and V form tw o different com pounds. In the first com pound, 24 g o f X com bine with
6 g o f Y. 60 a( by mass o f the second is X. W hat is the m ultiple proportion in these com pounds ? .?/#

E X A M P L E 6 . 5 U n d e r s t a n d i n g T h e L a w o f M u ltip le P r o p o r t i o n s
Problem : The elem ent X and Y combine to give two different compounds. 7 g of X and 2 g o f Y combine
to produce the compound XY. How many grams of Y combine with 7 g o f X to give the compound X 2Y 3 ?
Solution : _ In com pound XY
mx _ X _ 7
т^ ~Y~2

mx _ 2 X _ 2 x 7 _ 1 4 _ mx _ 7
In com pound X 2Y 3
mY 3Y
3Y 3x2 6 mY 3
The final ratio indicates that 7 g o f X com bines with 3 g o f Y to give 10 g o f X 2Y3.

EX E R C IS E 6.5 7 g o f the elem ent A and 16 g o f the elem ent В co m letcly com bine to give the c o m ­
pound A B2. If 10.5 g o f A and 18 g ol' В com letcly com bine to give another com pound, w hat is the form ula of
the second com pound ? A j/i.?

E X A M P L E 6 . 6 U n d e r s t a n d i n g G r a p h i c a l A n a ly s is
m e (g )
, I
Problem С : and H form two different compounds. The graph given
24f~ f . / / /И II aside shows the relationship between the masses of С and H in these com ­
pounds. If the formula of the compound represented by I is C 2H 4, what is
the formula of the compound represented by II ?
J2
Solution : From the graph we can read the grams of hydrogens com ­
9. bined with 18 g of C.
"Compound m e (g) т ц (g)]
( 1) C 2H 4 18 3

mH (g ) [(II) C xHy 18
We sec that the mass of hydrogen in the compound II is 4/3 times greater. (If equal masses of С are considered in
4J
both compounds.) If we assume x = 2 (the same as in the first compound, then, у is 4 x 4/3 = 16/3 or the em pir­
ical fonnula of the second compound will be:

C2H16/3 =* c 6Hi6 Щ
 Atomic Structure and Chemical Periodicity 193

6.1.3 LA W OF C O M B IN IN G VOLUMES
In 1808, Jo sep h G ay -L u ssa c rep o rted the relatio n sh ip s a m o n g the v o l­
u m es o f reactin g gases and th eir g aseo u s p ro d u cts. T he vo lu m es o f g a ses in ­
volved in a reaction, a t constant tem perature and p ressure, can be expressed as
a ratio o f sm a ll w hole num bers. F o r exam ple,
N 2 (g) + 3H 2 (g) -> 2 N H 3 (g)
1 volum e 3 volum es 2 volum es
1L 3L 2 L
T h e v o lu m e ratio, h o w ev e r, is g iv e n by the co effic ien ts o f the g ases in
the chem ical equation
I N 2 (g) + 3 H 2 (g) —> 2N H 3 (g)
T h e la w o f co m b in in g v o lu m es is ap p licab le o n ly to g ases. T h e sum o f
th e v o lu m e s o f the reactan ts m ay o r m ay n o t be e q u a l to the v o lu m e s o f the
g ases produced.
2 H 2 (g) + О 2 (g) —» 2H 20 (g)
2 v o lum es 1 volum e 2 volum es
T h ese in teg er relationships b etw e en reactin g gases and p ro d u cts sug g est
a p article m odel o f gases.
A m a d e o A v o g a d ro ex p la in ed the law o f co m b in in g v o lu m e s b y the
p rin cip le : e q u a l vo lu m es o f a ll g a se s a t the sa m e p re ssu re a n d tem p era tu re
contain eq u a l num bers o f m olecules. O n the contrary to D alton, w h o believed
th a t g a se o u s e lem en t co n sisted o f u n c o m b in e d ato m s, A v o g a d ro su g g ested
th a t som e g aseous elem en ts exist as diato m ic m o lecu les. T h u s, i f th e reactin g
p a rtic le s are really diato m ic m o lecu les, then th e ir ratio o f 2 to 1 m a tch e s the
v olum e ratio o f 2 to 1. T h is can b e illustrated as follow s.
2C O (g) + О 2 (g) 2 C 0 2 (g)
2 vo lu m es 1 v o lu m e 2 v o lum es
2 m olecules 1 m olecule 2 m olecules

EXAM PLE 6.7 Recognizing the Law of Combining Volumes

Problem : When 60 cm 3 o f NO is reacted with 20 cm 3 of 0 2 to give N 0 2, what will be the total volume
of the gases at the end o f the reaction if the temperature and pressure remain constant ?
Solution : The balanced equation representing the reaction is : 2NO (g) + 0 2 (g) —> 2 N 0 2 (g)
The coefficients o f the equation indicate that 2 cm 3 o f NO combines with 1 cm 3 o f 0 2 to produce 2 cm 3 of
N 0 2. Since the volumes of both reactants are given we should determine the limiting and excess reagent.
Volumes of gases : 2NO (g) + 0 2 (g) -> 2 N 0 2 (g)
Before reaction 60 cm 3 20 cm 3 0
Change in reaction - 40 cm 3 - 20 cm 3 + 40 cm 3
After reaction 20 cm 3 0 40 cm 3
Thus, the total volume o f gases at the end of reaction is (20 cm 3 of NO + 40 cm 3 o f N 0 2) or 60 cm3.
194 Chapter 6

EXER C ISE 6.6 a 100 cm 3 of mixture o f equal volumes of H2 and 0 2 gases is ignited to produce water
and then the system is cooled to the original temperature. What is the final volume ? 25 c m 3

EX E R C IS E 6.7 H ow many mL of N H 3 can be produced from the reaction of 20 mL of N 2 and 45 mL

of H 7 ? 3 0 m l.

6.1.4 C H E M IC A L E V ID E N C E FOR T H E E L E C T R IC A L
A n e le c tric c u rre n t is th e
flo w o f e le c tr o n s . I t is * N ATUR E OF MATTER : FA R A D A Y'S LAWS
m ea su re d in amperes (A ). W hen M ich ael F araday p erform ed his ex p erim en ts b ased on electrolysis
Q u a n tity o f e le c tric c h a rg e (d u rin g the 1830's ), D alto n p ro p o se d h is ato m ic th e o ry b u t no one h ad yet
is m e a su re d iri coulombs
su g g e s te d th e e x is te n c e o f e le c tro n s. F a ra d a y 's e le c tro ly s is e x p e rim e n ts
(C ). O n e c o u lo m b is d e ­
sh o w ed th at the q u antity o f electricity n ecessary to d e p o sit a g iv en w eig h t o f
fin e d as th e q u a n tity o f
e le ctricity c arrie d by a c u r­ an e le m e n t from so lu tio n s o f its d iffere n t co m p o u n d s w as alw ay s eq ual to a
re n t o f o n e a m p e re in o n e co n stan t o r som e sim ple m ultiple o f this constant. F o r exam ple, if electric c u r­
second. . ren t is p assed th ro u g h th ree electro ly tic sy stem s as sh o w n in F ig u re 6.1, the
1 С =r 1 A x s follow ing reactions w ill take place.

► Mg

molten NaCl molten MgCl 2 molten AI2 O 3

FIGURE 6.1 A n a p p a ra tu s re p r e se n tin g th e e le c tro ly sis o f m o lte n s a lts c o n n e c te d in s e r ie s

In cell 1, N aCl (1) N a (s) + 1/2 Cl 2 (g)

In cell 2, M g C l 2 0 ) -> M g (s) + C l 2 (g)

"weigTfts 0 i m e ta ls p ro d u ced are fo u n d to b e 0 .6 9 g o f N a, 0 .48 g o f M g and

0.27 g o f Al. T h e n u m b er o f m oles o f each m etal is :

" Na = r f 6/9 S 1 = °-03 mo1’ n M g = g , = °-02 m o l>n A i = — -27 g = 0 01 mol

23 g/m ol 24 g/mol A1 27 g/mol

The relation of these mole numbers by ratios is as follows :

Na : Mg : Al = 0.03 :0.02 : 0.01 = 3:2:1
194 Chapter 6

EXER C ISE 6.6 a 100 cm 3 of mixture of equal volumes of H 2 and 0 2 gases is ignited to produce water
and then the system is cooled to the original temperature. What is the final volume ? 25 cm 3

E X E R C IS E 6.7 How many mL of N H 3 can be produced from the reaction of 20 mL o f N 2 and 45 mL

of H 2 ? 5 0 m l.

6.1.4 C H E M IC A L E V ID E N C E FOR T H E E L E C T R IC A L
An electric current is the
flow of electrons. It is ‘ NATURE OF M ATTER : FA R AD A Y'S LAW S
measured in a m p e r e s (A ). W h en M ich ael F araday p erform ed his ex p erim ents b ased on electrolysis
Quantity of electric charge (d u rin g th e 1830's ), D alto n p ro p o se d h is a to m ic th eo ry b u t no one h ad y et
is measured in c o u l o m b s su g g e ste d th e e x is te n c e o f e le c tro n s. F a ra d a y 's e le c tro ly s is e x p e rim e n ts
(C). One coulomb is de­
sh o w ed th at the q u an tity o f electricity n ecessary to d e p o sit a g iv en w eig h t o f
fined as the quantity of
electricity carried by a cur­ an e le m e n t from so lu tio n s o f its d iffe ren t co m p o u n d s w as alw ay s equal to a
rent of one ampere in one co n stan t o r som e sim ple m u ltip le o f this constant. F o r exam ple, if electric cu r­
second. ren t is p assed th ro u g h th re e electro ly tic sy stem s as sh o w n in F ig u re 6.1, the
1 С =f 1 A x s follow ing reactions w ill take place.

*• M g

molten NaCl molten M gCl 2 molten AI2 O 3

FIGURE 6.1 A n a p p a ra tu s re p re se n tin g th e e lec tro ly sis o f m o lte n s a lts c o n n e c te d in s e r ie s

In cell 1, N aC l (1) -> N a (s) + 1/2 C l 2 (g)
In cell 2, M g C l 2 0 ) -> M g (s) + Q 2 (g)
in cell 3, A1 20 3 a ) -> 2 A1 (s) + 3/2 0 2 (g)
A fte r th e sam e am o u n t o f e le ctric ity is p assed th ro u g h th ese cells, the
w eig h ts o f m e ta ls p ro d u ced are fo u n d to be 0.6 9 g o f N a, 0.48 g o f M g and
0.27 g o f Al. T h e n u m b er o f m oles o f each m etal is :

n Na = ° '6 9 g = 0.03 m ol, n Mg= - M g-i - = 0.02 m ol, n A1 = - Q:?.7 § = 0.01 mol
23 g/m ol 24 g/mol 27 g/m ol

The relation of these mole numbers by ratios is as follows :

Na : Mg : Al = 0.03 :0.02 : 0.01 = 3 :2:1
 Atomic Structure and Chemical Periodicity 195

W ith in the ato m ic theory, this resu lt in d ic ate s that a ce rta in a m o u n t o f

electricity w ill deposit a fixed n u m ber o f atom s o r som e sim ple m ultip le o f this
num ber. T h erefore, an atom can carry only a fixed quantity o f charge. E lectric
charge com es from atom s in packages. T his m eans that electricity has a p artic ­
ulate nature. Since atom s carry electric charges, atom s m u st include th ese p a r­
ticles. T h e u n it particle o f electricity is n o w nam ed the electro n , sy m b o lized
by e \

FARADAY'S LAWS
T h e q u an tita tiv e relationships b etw een elec tricity and ch em ical c h an g e
w ere described by M ichael Faraday as follow s :

1. T h e w e ig h t o f a c h e m ic a l s u b s ta n c e d e p o s ite d a t a n e le c tr o d e is d ir e c t­
ly p r o p o r t i o n a l t o t h e a m o u n t o f c u r r e n t p a s s e d t h r o u g h t h e c e ll.
2. T h e w e i g h t s o f d i f f e r e n t s u b s t a n c e s p r o d u c e d b y a g i v e n a m o u n t o f
e le c tr ic ity a r e p r o p o r tio n a l to th e e q u iv a le n t w e ig h ts o f th e s u b s ta n c e s .

L e t's ex p la in F a r a d a y 's L aw s by th e e le c tro ly sis o f m o lte n so d iu m

chloride. S ince sodium chloride is an ionic com pound, the ions o f N a + and Cl"
are found in the m olten sodium chloride. In the case o f the electrolysis o f m o l­
ten sodium chloride, each sodium ion, N a+, is attracted to the cathode (the n eg ­
atively charged electrode) and gains 1 e" from the cathode and becom es neutral
sodium atom .
N a+ + 1 e" -4 Na
O r w e m ay describ e this eq u atio n as the com b in atio n o f one m o le o f so­
dium catio n s w ith one m ole o f electro n to form one m ole o f sodium atom . In
an electrolysis experim ent w e generally m easure the quantity o f charge in co u ­
lo m b s (ab breviated C )by m easu rin g the cu rren t in a m p eres, (A ) th at passes
through an electrolytic cell in a given period o f time.
Q uantity o f charge = Intensity o f current x tim e

T h e ch arg e o f o n e e le ctro n is 1.60 x 1 0 ' 19 C , th e n th e c h a rg e o f one

m o le o f electro n is ( 1 . 6 0 x l 0 19 C/e" x 6.02 x 10 23 e '/m o l) o r n early 96500 C.
T h e c h a r g e o f o n e m o l e o f e l e c t r o n , 9 6 5 0 0 C , i s u s u a l l y c a l l e d one F a ra d a y
(1 F) in o rd er to h o n o r M ichael Faraday, an E nglish chem ist and physicist.

1 m o le e- = 9 6 5 0 0 С = 1 F )

W e can sum m arize the q u an titav e relatio n sh ip s b e tw ee n electric charge

and the am ount o f m atter that is the deposited as follow s.
N a+ + 1 e" —> N a
1 m ol —> 1 m ol

9 6 5 0 0 С ^ 23 g
IF ^ 23 g
 196 Chapter 6

T he sam e relationships for the reaction taking place at the anode are:
2 0 —> O 2 + 2 e
1 m ol 2 m ol
71 g 2x96500 С
o r at S T P 22.4 L 2F

C o n sid er th e rection, N a + (1) + ё —> N a (1)

I f 1 F o f electricity (1 m ol o f electrons) is u sed, 1 m ol o f sodium , 23 g o f
N a, is p ro d u ced ; 2 F w o u ld lib e rate 2 m o l o f so d iu m , 4 6 g o f N a. S ince the
ch arg e o n th e so dium io n is 1 + , the e q u iv ale n t w eig h t o f sodium is the sam e
as the atom ic w eight.
1 eq u ivalent w eight o f sodium = 23 g

T h e rem oval o f 1 m ol o f electrons from the anode results in the discharge

o f 35.5 g o f c h lo rid e io n (1 m o l), th u s p ro d u c in g 0.5 m o l o f c h lo rin e gas,
Ci
2' 0.5 m ol o f chlorine gas = 1 gram eq u iv alen t = 35.5 g

I f 2 F o f electricity flo w th ro u g h the cell, 1 m ol o f C l 2 is p ro d u ced as in

O n e F alw ays lib e rate s one th e reaction below .
g ra m -e q u iv a len t o f elem en t 2СГ -> C l 2 + 2 ё
or com p o u n d . 2 m ol 2 m o l ё (= 2 F)
O ne fa r a d a y , then, w ill lib era te 1 g ra m -e q u iv a le n t o f an e le m e n t o r a
com p o u n d . In q u an titativ e p ro b lem s, w e c an use the fo llo w in g relationships
am ong m o l e , F, quantity o f electricity and gram equivalent.

( I m ol ё = 6 . 0 2 x l 0 23 ё = 1 F = 9 6 5 0 0 С = lg r a m - c q .o f an e lem en t?

E X A M P L E 6.8 C a lc u la tio n s a b o u t E le c tr o ly s is
Problem : A current of 1.93 A is passed for 20 minutes through an electrolytic cell containing molten
CuCl 2- Calculate the quantity o f products formed at the electrodes. Cu=63.5 g/mol Cl=35.5 g/mol
Solution : Since the quantities of products depend on the number of moles of electrons, therefore we should
first calculate the number of moles of electrons passed through the electrolytic cell.
(1.93 A, 20 min) —> ? С -» ? mol e' —> ? mol Cu -> ? g Cu

Q = I x t = 1.93 A x 20 min x 1.93 A x 1200 s = 2316 С

1 min
96500 С 1 mol e'
2316 С x 96500 }
x = _2316_ _ 0 024 mol e '

Now let us calculate the am ount o f products formed by 0.024 mol e". Since only the ions present in molten
CuCl 2 are Cu2+ and C l' then electrode reactions are as follows.
At the cath o d e:
C u 2+ + 2e' -> Cu
2 mol e" 1 mol 1
0 024 mol x mol j x ~ mol Cu =>0.012 mol Cu x 63.5 g/mol = 0.762 g Cu

Then 0.762 g o f Cu will be deposited at the cathode.

 Atomic Structure and Chemical Periodicity 197

At the a n o d e :
2С Г -> Cl2 + 2 e'
1 mol 2 mol
| x - 0.012 mol Cl2 => 0.012 mol Cl2 x 71 g/mol = 0.852 g Cl 2
x mol 0.024 mol

O r : 0.024 mol e" = 0.024 F. Since 1 F liberates 1 gram-eq of any species, then at the cathode 0.024 gram equiv­
alent of Cu2+, at the anode 0.024 gram-equivalent of СГ will become free.

1 gram- cq C u 2+ = — = 31.75 g => 0.024 g- cq of C u 2+ = 0.024 g - eq x 31/75 g = 0.762 g of Cu

2 1 g- cq
similarly

1 g- eq. C l = = 35.5 g => and 0.024 g- eq. of C l = 0.024 g - cq x 35-5 g = 0.852 g of C l 2 will be liberated.
1 1 g-cq

EXER C ISE 6.8 A lum inum is m anufactured by the e lec tro ly sis o f m olten A1 2 0 3 . C alcu late the quantities
o f the electr o ly sis products caused by the p assage o f 8 A for 1 hour through the electrolytic cell con tain in g m o l­
ten A 1 2 0 3 . 2.7gAl,2.4gO 2

EXERCISE 6 . 9 In the electrolysis of water, the reaction taking place at the anode is given by
2H20 (I) 0 2 (g) + 4H + + 4c-
Suppose 780 mL of 0 2 is collected at 27°C and 722 mmHg. How many faradays of electricity must have passed
through the solution ? How long would it have taken if the current had been 12A ? 0 . 121 ', 16.1 min

E X A M P L E 6 . 9 Q u a n t i t a t i v e P r o b le m s o n E le c tr o ly s is
Problem : If 200 mL of 0.3 M HgCl2 solution is clectrolyzed using 4.0 A for 20 min, what are the final
concentrations o f Hg2+ and Cl" remaining in the solution ? (Assume no change in volume)
Solution : First of all, we determine the mole number of Hg2+ and СГ ions present in the solution before and
after electrolysis.
Before electrolysis : п щ а 2 = ^.3 mol/L x 0.2 L = 0.06 mol =?• HgCl 2 (aq) -> Hg2+ (aq) + 2C1" (aq)
0.06 mol 0.06 mol 0.12 mol

During electrolysis : Q = I x t = 4A x 20 min x 60 s/min = 4800 С => 4800 С x 1 1X101 e = 0.05 mol e
96500 С

At the cathode : At the anode :

H g2+ + 2e" -> Hg 2СГ -> Cl2 + 2e"
1 mol 2 mol 1 2 mol 2 mol 1
05 mol СГ
x mol 0.05 mol J x ~ 0 025 mo1 Hg2+ x mol_________ 0.05 mol J *
0.025 mol o f Hg2+ will be removed from the solu- Then the passage o f 0.05 mol e' from the solution
tion as Hg. Thus, the mole number o f Hg2+ ions re- removes 0.05 mol o f Cl" ions, and the solution
maining in 200 mL o f solution is (0.06-0.025) or contains (0.12-0.05) or 0.07 mol of Cl". Its concen-
0.035 mol. And the concentration o f Hg2+ ions is: tration in the solution is:

[Hg2*] = — = °-035 mo1 = 0.175 M [C l] = — = 0 '07 mo1 = 0 .3 5 M

1 6 J V 0.2 L V 0.2 L
198 Chapter 6

EXER C ISE 6. 10 a constant current of 9.65 A was passed through a 250 mL solution of 2M Cu2+ for l
hour. Calculate the concentration of Cu"+ in the solution at the end of electrolysis. How many hours will it take
to deposit all the C u2f in the solution by the same current ? 1 . 2 SM, 2 . 7 8h

EXER C ISE 6.11 How many amperes o f current are required to dcpositc 9.6 g of magnesium in 4 x I0 4
seconds from m olten M gCl 2 ? 1.93A

E X A M P L E 6 . 1 0 Qua nt it at i ve P ro b le ms on Electrolysis
Problem : A given quantity of electricity passes through two electrolytic cells connected in series. One con­
tains molten M gCl2 and the second molten AICI3. If 4.8 g o f Mg is deposited in the first cell, how many grams
o f aluminum will be deposited in the second cell ?
Solution : W hen two electrolytic cells are connected in series, the number o f electrons passing through each
cell is the same. Then, we can find the number of moles o f electrons necessary to deposit 10.8 g o f Mg.
10.8 g Mg => 10.8 g/24 g/mol = 0.45 mol Mg T h e n u m b e r o f g -e q u iv a le n ts (e) o f d ifferen t
2+ sp e c ie s d e p o s ite d b y a g iv e n q u a n tity o f
Mg + 2e' —> Mg
e le c tric ity is the sa m e. T h e re fo re :
2 mol 1 mol
0.90 mol e' EM g = eai
x mol 0.45 mol 1 0 -8 g
0 .9 eq
£ме 1 2 g / 1 eq

The am ount o f Al deposited by 0.90 mol e" is: £ A1 = 0 .9 e q = > 0 .9 e q x

eq
Al 3+
1
3e -> Al
3 mol 1 mol
] r = 0 .3 mol Al => 0.3 mol Al x 27 g/mol = 8.1 g Al
0.90 mol x m ol

EXERCISE 6.12 A given quantity of electricity flows through two separate electrolytic cells containing
solutions of SnCl4 and C u S 0 4 respectively. If 3.84 g of copper is deposited in one cell, how many grams of tin
are deposited in the other cell ? Cu=64, S n - 1 19 J.57 g

EXERCISE 6.13 The same quantity of electricity that liberated 12.96 g of silver was passed through an
aqueous solution o f platinum salt, and 7.8 g of platinum was deposited. Calculate the charge on the platinum
ions in this solution. Pt=195 Ag=108 3+

6.2 CHANGING CONCEPTS OF ATOM

In 1805, J o h n D alton proposed his atom ic m odel and laid the founda­
tions o f m odem atom ic theory. C hem ists in the fo llo w in g decades set them ­
selv es the task o f im proving the Dalton's m odel. In the light o f the numerous
experim ents, Dalton's m odel w as finally abondoned. B ecause it becam e clear
that atom s w ere d ivisible under special conditions, and w ere com posed o f
three fundamental particles; electrons, protons, and neutrons. W e w ill now e x ­
amine the discoveries o f these fundamental particles. .
 Atomic Structure and Chemical Periodicity 199

6.2.1 D IS C O V E R Y OF TH E ELEC TR O N
F arad ay's quantitative investigations on electrolysis gave the first e x p eri­
m ental evidence that electricity m ig h t exist as discrete particles. A s m entioned
in se c tio n 6 .1 .4 , th e resu lts o f F a ra d a y 's e x p e rim e n ts su g g e ste d th a t th ere
m ust b e so m e fu n d am en tal u n it o f electricity associated w ith ev e ry atom . T he
e ffectiv e stu dies on the effect o f electricity on m atte r w ere w ith gas d ischarge
tubes. T h e se g lass tu b es co n ta in a gas u n d e r lo w p re ssu re (a b o u t 0.01 a t­
m osphere) and they are fitted w ith m etal w ires called electrodes. W hen a h ig h
voltage (about 10 4 V ) is applied across these electrodes, som e so rt o f radiation
m o v es from the n e g a tiv e ly ch a rg ed w ire, c alled th e c a th o d e , to the o ther,
called th e a n o d e. See F igure 6.2. T h is ra d iatio n w as called ca th o d e rays.
C athode rays w ere found to consist o f a stream o f particles. T he particles
FIGURE 6.2 A cathode
in th e c a th o d e ray w ere n eg ativ ely ch arged. B ecau se they are d eflecte d from
ray tube with perpendicular
electric and m agnetic th e ir u su al straig h tlin e p a th to w ard a p o sitiv ely ch arg ed p late. C ath o d e rays
fields. In the absence of did n o t d ep end on the gas in the tube o r the m etal in the electrodes. T h is m eant
electric and magnetic field, that the p articles in cathode rays w ere in all m atter. T h e y w ere subatom ic p a r­
beam of rays flow from ca­ tic le s and w ere nam ed e lec tro n s.
thode to the anode. When
only electric field exists, A s sh o w n in F ig u re 6.2, J.J. T h o m so n stu d ied the b e h a v io r o f cath o d e
the cathode ray particles ray s p a ssin g th ro u g h b o th a m ag n etic field and electric field. In 1897, he d e ­
curves toward the positive term ined the value o f e/m fo r the electron, and found to be -1.76 x lO 8 C/g
plate. J.J. Thomson m eas­
T h e ch arg e o f the electro n w as m easured b y R o b e rt A .M illik an in 1908.
ured the deflection of ca-
thode-ray particles (elec­ T h e c h a rg e on a single e le ctro n is -1 .6 0 2 2 x 10 "19 С
trons) in both magnetic and T h e m ass o f the electron can be calculated from the v alu e o f e/m and the
electric field and calculated
v alu e o f e \ _19
the charge to mass ratio of m = _ e _ = -1.6022 x 10 С = 9 10 x 10‘28 g
electrons. He found e/m to
be identical for all particles л e/m - 1 . 7 6 x l 0 8C/g
irrespective of the kind of
gas in the tube.
6.2.2 D IS C O V E R Y OF T H E P R O TO N
A fte r the d isco v ery o f the ele ctro n , gas d isch a rg e tu b es w ere m o d ified
[— Perforated cathode for ad d itio n al ex p erim en ts. In one series, the cath o d e w as shaped lik e a d isk
Anode
w ith a h o le in its ce n te r and the tu b e's in n e r su rface b eh in d th e c ath o d e w as
coated w ith phosphorus.
I f the cath o d e in a gas discharge tube had holes in it as sh o w n in F igure
6.3, so m eth in g w as m o ving through the hole in the cath o d e, in a d irectio n o p ­
p o site th a t o f the c a th o d e ray. It w as ob serv ed th a t a stream o f p articles w as
m o v in g th ro u g h th e h o le in the c a th o d e and th e se p a rtic le s h a v e p o sitiv e
charge. P o sitiv e particles o f this type (p o sitive ions) are fo rm ed in an electric
d isch arg e tu b e w hen cath o d e rays rem ove e lectro n s from the ato m s o r m o le ­
c u le s o f th e gas p re se n t in the tu b e. T h e se stre am s o f p o sitiv e io n s, called
p o sitiv e r a y s, cau se th e p h o sp h o ru s to glow .
FIGURE 6.3 G o ld s t e in ,
u sin g a m o d ifie d c a th o d e T h e d eflections o f positive rays in electric and m agnetic fields w ere stu d ­
ray tu b e, d is c o v e r e d ra y s ied b y J.J. T h o m so n in 1906, and the v alu es o f e/m w ere d e te rm in e d fo r the
travelling in th e o p p o s ite p ositiv e rays.
direction o f c a th o d e rays.
200 Chapter 6

W h en d iffe re n t gases are used in the d isc h arg e tu b e, d iffe re n t types o f

p o sitiv e io n s arc form ed. W hen h y d ro g en gas is used, a p o sitiv e p a rtic le re ­
sults that has the sm allest m ass o f any positive ion observed.
e /m = + 9.579 x 10 4 C /g
T oday, w e call th ese p articles p ro to n s , and accep t them a co m p o n en t o f
all atom s.
T h e ch arg e o f proton is equal in m agnitude to th at o f the electron b u t o p ­
p osite in sign.
e = +1.6022 x K b 19 С
T h is ch a rg e is called the u n it e le c tric a l c h a r g e
T h e m ass o f th e proton, w hich is 1800 tim es the m ass o f the electro n , can be
calculated from the value o f e /m and the value o f e.

e +1.6022 x 10 19 С , , n -24
m = = -------------------------- = 1.6726x 10 g
p/m 4
1 +9.579 x 10 C/g
Positive charge spread
over the entire sphere
6.2.3 T H O M S O N 'S A T O M IC M O D E L
A fter d eterm ining the charges and m asses o f the v arious ions, and o f the
electron, n ew q u estions arose. H ow are the p o sitive and neg ativ e p articles ar­
ranged in the atom s ? W hat is the design or structure o f the atom ?
J . J . T h o m s o n pro p o sed th e first d e tailed ato m ic m odel. A cc o rd in g to
his m odel, atom s w ere com posed o f positively charged protons and negatively
ch a rg e d electro n s. In a n eu tral atom , the n u m b e r o f p ro to n s is eq ual to the
n u m b e r o f electrons. T h e a to m w a s a sp h e re o f p o s itiv e e le c tric ity in w h ic h
e le c tro n s w e re e m b e d d e d lik e ra is in s in a cake. F ig u re 6.4 show s T h o m so n
FIGURE 6.4 T h o m s o n 's m ° d c l f ° r atom . E ven though T h o m so n 's m odel w as an im p o rtan t step in the
m o d e l o f atom , s o m e tim e s g ro w th o f the ato m ic m odel, it w as n o t useful in p red ic tin g o r ex p lain in g the
d e s c r ib e d a s th e ra isin p roperties o f the atom .
m uffin m odel.

6.2.4 R U T H E R F O R D 'S A T O M IC MODEL

R u th e r fo r d did n o t th ru st T h o m s o n ’s m o d el. T h e re fo re , R u th e rfo rd
and his co-w o rk ers initiated a scries o f experim ents in w hich v ery th in foils o f
g o ld and o th e r m etals ( 10-4 cm to 1 0 '5 cm th ick ) w ere used as targ ets fo r a
particles derived from a radioactive substance. S ee F ig u re 6.5. T h e radioactive
su b stan ce w as en closed in a lead co n ta in e r in su ch a w ay th a t o n ly a n arro w
beam o f a particles could escape. T he alpha particles are detected by the lig h t
th e y p ro d u c e w h en th ey c o llid e w ith a scin tillatio n screen. T h is sc ree n is a
plate covered w ith zinc sulfide.
T h e fo llo w in g o b s e r v a tio n s w e r e r e p o r te d b y R u th e r fo r d :
1. The large m ajority o f the a p a rticles p en etra ted the m eta l fo il undeflected.
2. S o m e o f a p a rticles, h ow ever, w ere deflected fr o m their straight-line path.
3. A f e w re c o ile d b a ck to w a rd s their so u rce .
 Atomic Structure and Chemical Periodicity 201

FIGURE 6.5 (a) T h e e x p e rim e n ta l d e sig n o f R u th erfo rd 's m e a s u r e m e n t o f sca tte rin g o f a p a rtic les b y a p ie c e o f
g o ld foil. M o st o f th e a p a rticle s p a s s d irectly through th e foil w ithout a c h a n g e in direction, b u t s o m e w ere d e ­
flected. Incredibly a fe w o f th e p a rticles w ere re fle c te d b a c k , (b) T h e re su lts o f th e a p a rticle sc a tte rin g e x p e ri­
m e n t m a y b e e x p la in e d b y m e a n s o f n u c le a r a to m m o d e l p r o p o s e d b y R utherford. T h e a p a rticles with +2 ch a rg e
are re fle c te d o r d e fle c te d w h e n th e y collide with or p a s s c lo s e to th e m u c h h e a v ie r g o ld n u c le u s (+79 charge).
S in c e th e n u c le u s is ve ry sm all, c o m p a r e d to th e s iz e o f a n a to m , very fe w p a rticles s h o w re fle ctio n s o r d e fle c ­
tio n s.
R u th e rfo rd ex p lain ed the resu lts b y p ro p o sin g h is ato m ic m odel.
A c c o r d in g to R u t h e r f o r d 's a to m ic m o d e l:
1. M o st o f the m ass a n d all o f the po sitive charge o f an atom are co n cen tra ted
in a very sm a ll reg io n , w h ich R u th e rfo rd te rm e d the n u c le u s . T he a to m is
m o stly e m p ty space.
2. The m a g n itu d e o f the charge on the nucleus is differen t f o r d ifferen t atom s.
3 . The electro n s are o u tsid e the n u cleus a n d o ccupy m o st o f the to ta l vo lu m e
o f the atom . The po sitive charge o f the nucleus equals the to ta l negative charge
o f a ll the e le c tro n s in an elec trica lly n e u tra l atom . T he n u m b e r o f p ro to n s,
c a lle d a to m ic n u m b e r , is eq u a l to the n u m b e r o f electro n s p r e s e n t in the
atom , i f it is neutral.

6.2.5 T H E D IS C O V E R Y OF N E U T R O N ,
In th e early 1930 s, R utherford and o th er scientist predicted the existence
o f a n o th e r ty p e o f su b ato m ic p article in the n u c leu s o f the atom . S in ce lik e
ch a rg e s rep el each o ther, th e pro to n s in the n u c leu s w ould repel ea ch o ther,
and th erefo re the nucleus w ould be unstable. H ow can a n u m b e r o f p o sitiv ely
ch arg ed p articles be co n fin ed in a tin y v o lu m e o f n u cleu s ? T h e re sh o u ld be
so m eth in g to hold these p ro to n s in the nucleus. T h is p article w as d etected by
th e E n g lish P h y sic ist J a m e s C h a d w ic k in 1932. H e d e te rm in e d th e e x is­
ten ce o f un ch arg ed p articles ( n e u tro n s ) in the n ucleus. N eu tro n s w ere d e ter­
m in ed to have a m ass slightly greater than protons.
T h e basic particles present in an atom are sum m arized in T ab le 6.1.
202 Chapter 6

T A B L E 6.1 P ro p e rtie s of S u b a to m ic P a rtic le s.

In re c e n t y e a rs a la rg e
n u m b e r o f s u b a to m ic r ss charge ’ л
p a rtic le s h a v e b e e n d is ­ Panicle real (g) unit real (C) unit
c o v e r e d b y p h y s ic is ts .
B u t c h e m ists d e a l o n ly Proton (p) 1.672x1 O'24 1 + 1.602x10-19 +1
w ith th e s e th re e fu n d a ­
Neutron (n) 1.675x1 O'24 1 0 0
m e n ta l p a r ti c l e s e le c ­
tro n s, p ro to n s, a n d n e u ­ Electron (e') 9 109x10‘28 1/1852 -1.602x10 '19 -1
tr o n s .

E X E 6 .1 4 The element osmium, has the highest density of 22.6 g/cm 3. The nucleus of the osm i­
um atom has 76 protons and 1 14 neutrons. Assuming that the radius o f the nucleus of the atom is 5 x 10 '5 A°
(1 A° = 10 cm), calculate the density of the nucleus of the osmium atom. Compare your result to the density
of osmium atom ? 6 . 0 7 x 1 0 14 g / c m 3

6.2.6 A T O M IC N U M B E R A ND A T O M IC M A S S N U M B E R
F o r a g iv en elem en t the n u m b e r o f p ro to n s do n o t v a ry , b u t the n u m b er
o f n e u tro n s m a y v ary w ith in a lim ited range. S ince the id e n tity o f an atom is
determ ined prim arily by its proton num ber, the p ro to n n u m ber o f an elem ent is
ca lle d the a to m ic n u m b e r (show n by Z ) o f the elem ent.

^A to m ic n um ber = proton n u m b e r ^

s___________ z = P у

F o r a n e u tra l atom , the n u m b er o f p ro to n s and the n u m b e r o f electro n s

arc equal. T h u s, for a neutral atom

atom ic n u m b er = proton n u m b er = electron n u m b e r

Z = d = e
T h e total m ass o f an atom is p rim arily determ ined by the total n u m b er o f
p ro to n s and n eu tro n s in its nucleus. The to ta l n u m b er o f n eutrons a n d p ro to n s
in the n u cleu s o f an atom is c a lle d tjhe a to m ic m a s s n u m b e r (sh o w n by A).

atomic mass T h e ato m ic n u m b e r and atom ic m ass n u m b e r o f an e le m e n t that h a s a

number sy m b o l o f X m a y b e show n by £ x . F o r ex am p le the iro n atom h a s 26 p ro ­
t to n s and 3 0 neutrons, its sym bolic representation is ^ F e .
A v 4 -» charge
I f an a to m g a in s o r lo ses e lec tro n s an io n is fo r m e d . In th a t case the
ZA
charge (q) o f the ion is:
4
atomic number charge = pro to n n u m b er - electron n um ber

p
 Atomic Structure and Chemical Periodicity 203

I f a n e u tra l atom g ain s n T h e ch arg e o f th e io n m ay be included in th e sy m b o l lik e £ x q . F o r e x ­

e le c tro n s , it g a in s (n -) am p le i f n eu tral iro n atom loses 3 electro n s, th e n it p o ssesses 26 p b u t (26-3)
charge. I f it lo se s n e le c ­ o r 23 electrons. T h e charge o f the ion produced is
tro n s, it g ain s (n+ ) c h a r­
q = p - с => q = 26 - 23 = 3 o r 3+
ge-
Its sy m bolic representation is: ^ c3+

E X A M P L E 6.11 D e te r m in in g F u n d a m e n ta l P a r tic le s in A to m s a n d Io n s
Problem : Indicate the atomic number, atomic mass number, the number o f protons, neutrons and electrons
in each o f the following species. a ) ,^ N e b )t^ A l c) ^ C a 2+ d ) 23A r3
Solution :
a) The comparison o f the symbol £ x with 2[Nc reveals that the atomic number is 10, so neon has 10 protons.
The number of electrons in neutral atoms is the same as the number of protons, that is 10. The mass number is
21, so the num ber of neutrons is 21-10=11.
b) Atomic number = 13 => proton number = 13 => electron number = 1 3
Atomic mass number = 27 => Neutron number = 27-13=14
c) Z = 20, p = 20 and q = p - e => с = p - q = 20 - (+2) =18, A = 40, n = A - Z = 20
d) Z = 33, p = 33, and q = p - e = > e = p - q = 3 3 - (-3) = 36, A = 75, n = A - Z = 75 - 33 = 42

E X ER C IS E 6.15 Indicate the number of protons, neutrons, and electrons in each of the following spc-
, lu , , 65-, л 80d 1- i\lw u 2+
cics. a) j H b) 30Zn cb 5 ^ 80Hg

E X A M P LE 6.12 C a lc u la tio n s B a sed on A to m ic an d M a ss N u m b e r s

Problem : Л р х 3* ion has 28 electrons. How many neutrons are there in its nucleus ?
Solution : If X3+ has 28 electrons, X has 3 1 electrons. Because X3+ ion is formed by the loss o f three elec­
trons. W hen an atom is neutral, the no o f protons equals the no o f electrons. O rq = p - e = > 3 = p - 2 8 = > p = 31
In this example, the neutral X atom has 31 electrons and 31 protons. The number o f neutrons is :
A = p + n = > n = A - p = 7 0 - 3 1 = 39

E X E R C IS E 6.16 56 x 2+ has 30 neutrons. How many electrons does it have? 24

EXAM PLE 6.13 C a lc u la tio n s B a se d o n S u b a to m ic P a r tic le s

Problem : X2+ and Y3' have the same number of electrons. (They arc isoeleclronic) If the atomic number of
Y is 7, what is the atomic number of X ?
Solution : First, we find the number of electrons of Y3'. The proton number of Y is 7, then, the num ber of
electrons in Y 3'i s : q = p -e e = p - q = 7 - (-3) = 10
X2+ has 10e" too. Its proton number, or atomic number i s : q = p - e = > p = q + e = + 2 + 1 0 = 1 2

E X E R C IS E 6.17 x 3+ and Y3' have the same number of electrons. If the atomic no of Y is 15, what is
the atomic number of X ? 21
204 Chapter 6

EXAMPLE 6.14 C a lc u la tio n s B a se d on S u b a to m ic P a r tic le s

P ro b lem : 0.1 mol of M gX 2 weighs 6.2 g. If the atomic num ber o f X is 9, how many neutrons does X
have? Mg = 24
Solution : The m olecular weight of M gX 2 is : n = => MW = — = = 62 g/mol
MW n O.l mol

MgX 2 = 62 =? 24 + 2X = 62 => X = 19 (the mass number)

The atomic weight is equal to the mass number. => A = p + n => n = A - p (or Z) = 19 - 9 = 1 0

EXER C ISE 6.18 0 .25 mol X ,C i weighs 36 g. If the proton number of X atom is one less than its neu-
v 3+ 11
iron number, determine the number of electrons in X . f“C itie '

E X A M P L E 6.15 C a lc u la tio n s B a se d on S u b a to m ic P a r tic le s

Problem : XO^" has 48 neutrons and 50 electrons. Find the atomic number and atomic mass number of the
element shown by X ?
0
S olu tio n : If XO' ’ were neutral (XO 4) it would have 50 - 3 = 47 electrons. In a neutral oxygen atom, there
arc 8 electrons and 8 neutrons then, four oxygen atoms contain 4 x 8 = 32 electrons and 32 neutrons. The num ­
ber of electrons in a neutral X atom is 47 - 32 = 15. Then for neutral X atom p = e = Z = 15. The number of
neutrons in the X atom is 48 - 32 = 16
and A = p + n = > A = 15 + 16 = 31

E X E R C IS E 6 .19 X -,0 ‘ has 112 neutrons and 106 electrons. What arc the atomic number and atomic
mass number of the element X ? 24, 52

6 .2 .7 IS O T O P E S
In 1912, J.J .T h o m so n d e sin g e d so m e e x p e rim e n ts to d e te rm in e the
ch arg e - to m ass (e/m ) ratios o f po sitiv e ions. H e obtain ed u n ex p ected results
w ith n e o n gas. T h e ele m en t n eo n con tain ed at le a st tw o k inds o f atom s. O ne
h ad a m o la r m ass o f 20 gram , and the o th e r 22 gram . S ee F ig u re 6 . 6 .

A ccelerating - .
plates.

E lectron
beam

( 1—
Sample
gas

FIGURE 6.6 A d e v ic e c a lle d m a s s s p e c tr o m e te r is u s e d to d e te r m in e th e e x is ­

te n c e o f th e d ifferen t m a s s e d a to m s o f th e s a m e e le m e n t. N e o n a to m s are b o m b a rd ­
e d with a ve ry high s p e e d elec tro n s, c a u sin g th e n e o n a to m to lo s e a n electron. T he
resu ltin g N e + io n s are a c c e le ra te d through a n electric field a n d s e n t into a m a g n e tic
field. U n d e r th e in flu e n c e o f m a g n e tic field e a c h N e + follo w s a circular p a th c o n s is ­
te n t with its m a s s . L ighter N e + io n s follow a sm a lle r c u rv e d p a th , h e a v ie r o n e s a larg­
e r p a th .
 Atomic Structure and Chemical Periodicity 205

L a te r it w as found tfffit the ato m s o f the sam e e le m e n t did n o t alw ay s

have th e sam e n u m b e r o f neutrons. F o r ex am p le th ere are th ree ty p es o f o x y ­
g e n ato m s and they differ only in th e ir n u m b e r o f neutrons. A to m s h a vin g the
sam e num b er o f p ro to n s (atom ic num ber) b u t differen t n u m ber o f neutrons (or
atom ic m ass n u m ber) are ca lled iso to p e s. It is cu sto m ary to id en tify isotopes
by m ass n u m b ers only, su ch as О - 16, О - 17, and 0 - 1 8 . L e t us c o m p are
the n u m b er o f subatom ic particles in th ese isotopes.

( л
Isotope Z A P n
Hydrogen has three iso­
topes:
0 -1 6 or ^ 0 :: 8 16 8 8
H -l or ordinary hydrogen,
H-2 or deuterium, and 0 -1 7 o r ’J o 17 9
8 8
H-3 or tritiu m
0 -1 8 o r ’V) 18 8 10
^ 8 J

As w e see later, the chem ical properties o f an elem ent are prim arily deter­
m ined by the n u m b er o f protons and electrons, therefore the isotopes o f an ele­
m e n t h a ve sim ila r c h em ica l p ro p erties, b u t slig h tly d iffe ren t p h y s ic a l p ro p e r­
ties.
W e encounter a problem w h en w e try to determ ine atom ic w eights o f ele ­
m en ts th at h av e isotopes. F o r exam ple; w h ic h w ill be th e ato m ic w eig h t o f
o x y g en ; 16, 17 o r 18 ? T h e pro b lem w as settled by in tro d u c in g a w e ig h te d
a v era g e concept. T h e w eig h ted average m ass o f an elem e n t d ep en d s o n b o th
n a tu ra l a b u n d a n c e s o f iso to p e s and the a to m ic m a sse s o f iso to p e s. T h e
w eig h ted av erage is obtained by m u ltip ly in g the atom ic m ass o f each isotope
by its fraction abundance, and adding the values obtained.
(^ A to m ic w e ig h t = ^ (fr a c t io n a l a b u n d a n c e ) x A to m ic m a ss ^

E X A M P L E 6.16 F in d in g th e A to m ic W eigh t o f an A to m
Problem .'Natural magnesium is found to contain 78.6 % Mg-24, 10.1 % Mg-25 and 11.3 % Mg-26. C alcu­
late the weighted average mass of Mg atom.
Solution ; Atomic weight = I (fractional abundance) x mass
AW (average) = — x 24 + — x 25 + — x 26 = 24.33
_________________________ 100___ TOO________ 100_______________________________________________

EXERCISE 6.20 Naturally occuring boron consists of 80.4 % B -ll and 19.6 % B - 10. Calculate the av­
erage atomic mass of boron. 1 0 .8

E X E R C IS E 6.21 The clem ent chlorine consists of two isotopes whose atomic masses are 35 and 37.
What arc the natural abundances of these two isotopes if the average atomic mass of chlorine is 35.5 ?
H in t: Let the percentage abundance of Cl-35 be x , then, the percentage abundance of Cl-37 will be 100-л:.
75% and 25%
206 Chapter 6

EXER C ISE 6.22 Fill the gaps in the following table, and indicate the species that are isotopically relat­
ed. .... , , ......A
12r 27A13+ 16o 2- ;Q? ?t -
6^ 13 8 У
p 13
n 15 12
e 12
Z

A 28
Net charge 4+ 0 2+
i Nuclear charge 14+
................ ....f
6.3 BOHR'S ATOMIC MODEL
R u th erfo rd 's n u clear atom m odel, w ith an ex trem ely tiny, m assiv e n u c le ­
u s su rro u n d ed b y a sea o f electro n s, ex p lain ed nicely th e p ro p e rtie s o f atom s
rev ealed b y the d ischarge-tube experim ents, a -p a rtic le scatterin g experim ents
and th e ex isten ce o f isotopes. B u t there w as a serious co n tra d ic tio n w ith R u ­
th e rfo rd 's m o d e l. S in c e th ere is an a ttra c tiv e fo rc e b e tw e e n th e p o sitiv e ly
ch arg ed n u cleu s, and the neg ativ ely charged electrons, the electro n s w ould be
ex p ected to fall into the nucleus. I f th ey w ere in c irc u lar m otion, th e ce n trifu ­
gal force (m u 2/r) acting on the electrons w ould keep them being draw n into the
n u cleu s. S ee F ig u re 6.7. H o w ev er, acco rd in g to cla ssic al p h y sics, an electro n
(or any charged particle) m oving in a circular orbit w ould radiate energy conti-
FIGURE 6.7 If e le c tr o n s n o u sly ; and th is en e rg y lo ss w o u ld c au se e le c tro n to m o v e in sm a lle r and
ro ta te in circular orb its th e sm aller orbits and finally fall into the nucleus, and atom w ould collapse.
attraction fo rc e o f n u c le u s
o n a n electro n (F p , is b a l­ In 1913 N iels B o h r, a D an ish scientist, a ttem p ted to reso lv e this ap p a r­
a n c e d b y th e c e n tr ifu g a l e n t p a ra d o x b y su g g estin g a n ew th eo ry fo r the b e h a v io r o f m atter. H e p ro ­
force acting on it (F 2). p o sed th a t th e en erg y o f an electron in an atom c a n n o t vary co n tin o u sly b u t
q u a n tize d (restricted to d iscrete, o r ind iv id u al v alues). T h e success o f B ohr's
th eo ry in ex p lain in g the structure o f lig h t em itted by hyd ro g en atom o r h y d ro ­
gen-lik e ions (ions th at have only one electron such as 2H e+ o r 3L i2+) led to its
g en eral accep tan ce. B efore discu ssin g B ohr's assu m p tio n s ab o u t the b e h av io r
o f electrons in atom s, le t us exam ine the beh av io r o f light.

6.3.1 L IG H T
E le c tro m a g n etic rad iatio n , su ch as radio w av e s, in frare d ra d iatio n , X
rays, g am m a rays, cosm ic rays (in clu d in g light) is the em issio n o r tra n sm is­
sion o f e n erg y in the form o f w aves. L ig h t is a form o f energy o r e lec tro m a g ­
n etic radiation. It has a dual nature: w a v e n a tu r e and p a r tic u la te n a tu r e . A
w av e can be co n sidered as a v ib ratin g d istu rb an ce by w h ic h en erg y is tra n s­
m itted. The fu n d a m e n ta l p ro p e rtie s o f a w a ve are its w a ve len g th , fr e q u e n c y ,
speed, a n d energy.
1. W a v e le n g th (X , lam bda) is the dista n ce b etw e en id e n tic a l p o in ts on
 A t o m i c S t r u c t u r e a n d C h e m i c a l P e r i o d i c i t y 2 07

su c c e ssiv e w aves. O r it is the distan ce from c re st to c re st o r tro u g h to trough.

S ee F ig u re 6 . 8 . W av elen g th is ex p ressed in u n its o f length. D ep en d in g on the
ty p e o f ra d ia tio n th e w a v e len g th m a y be E xpressed in u n its o f m , cm , m m ,
p m , n m ( l n m = 10'9 m) o r A ° (A n g stro m , 1A ° = Ю'10 m ).
2. T he n u m b er o f the w a v e crests (o r tro u g h s) th a t p a s s th rough a g iv en
p o in t in o n e se c o n d is c a lle d frequency (f). F re q u e n c y c an b e ex p ressed by
the units cy cle/seco n d , 1/s, o r H ertz (H z).
3. In a vacuum , a ll fo r m s o f electrom agnetic radiation travel a t the sam e
s p e e d , 3 .0 x 1 0 s m/s. T h is sp eed is c alled the speed o f light a n d s y m b o l­
ized b y c. T h e w avelength and frequency are inversely proportional to one an­
other. ( f a l A ) T he p roduct o f A,xf is eq ual to the speed o f light.
FIGURE 6.8 T h e d is ­
ta n c e b e tw e e n id e n tic a l
p o in ts, s u c h a s c o n s e c ­
ED •
E v e n th o u g h d iffe re n t form s o f electro m ag n etic rad iatio n h av e d ifferen t
utive p e a k s (or tro u g h s)
w avelengths and frequencies they all have the sam e speed in a vacuum .
is th e w a velen g th .
4. E le ctro m ag n etic rad iatio n has also p articu la te nature. It is em itted by
T h e s p e e d o f lig h t d e ­ m a tte r in d isco n tin u o u s u n its called photons . T h e en ergy o f a p h o to n m ay be
p e n d s o n th e m e d iu m
determ ined from the expression
th ro u g h w h ic h it tra v e ls .
I t h a s th e g re a te s t v a lu e (E = h f)
in v acu u m o r space.
w h e re h is *PIanck's constant, 6 . 6 3 x l 0 '34 J.s o r 1 .5 9 x l0 "37 k c a l.s ,
o r 9.54 x 10'14 kcal.s/m ol, and f is th e fre q u e n c y (1 /s). S in c e tacf = c,
then f= c A . So w e m ay w rite :
Г е = |1 f = h

E X A M P L E 6.17 C alculating W avelen gth and E nergy from F requ en cy

Problem : Turkish third radio station (TRT III) broadcasts at a frequency of 98 M Hz. Calculate (a) the wave­
length of this radio waves in meters, (b) the energy o f one mole o f photons of this radiation. g
Solution : a) f = 98 M Hz = 98 x 106 1/s As noted above ^.xf = с or X = - = .3 x 10 m /s s 3 j m
f -- 6
98 x 10 1/s

b) E = h f = 9.54 x 10 ‘14 kcal.s/mol x 98 x 106 1/s = 9.4 x 10'6 kcal/mol

E X E R C I S E 6 . 2 3 W hen lithium metal is heated, photons of red light with a wavelength of 671 nm arc
emitted. W hat is the frequency and energy in kcal/mol o f this light? 4 .5 x 1 0 14 Its, 42.9 kcal/m ol

6.3.2 ATOM IC SPECTRUM

W h en su n lig h t (o r w h ite lig h t from a g lo w in g solid) is passed th ro u g h a
p rism , it is se p arate d into co lo red b an d s ran g in g from red to v io le t. In this
band, th ere is a gradual, and continual change from one co lo r to the n ex t as w e
see in th e rain b o w . T h is c o m p lete array s o f co lo rs fo rm a continous spec­
trum . S e e F ig u re 6.9. S in ce e a c h c o lo r c o rre sp o n d s to a sp e c ific en erg y ,
then, su n lig h t co n tain s all the en erg ies o f visible light. S u n lig h t also co n tain s
in v isib le lig h ts to h u m an eyes such as ultraviolet (v ery h ig h freq u en cies) and
infrared (v ery low freq u en cies) light. S ee F ig u re 6.10. T h e y ca n be detected
and reco rd ed w ith instru m en ts called spectrograph.
*Max Planck (1858-1947) A German physicist, and founder of quantum theory. The energy o f electromagnetic radiation (including
light) is composed o f certain discrete amounts (or quanta), which is calculated by the formula E=hf.
208 Chapter 6

C ardboard W hite
with slit c ardboard

Red
Orange
Yellow
G reen Spectrum
Blue
Indigo
Violet

FIGURE 6.9 W h e n su n lig h t is p a s s e d through a p rism it p r o d u c e s a c o n tin o u s sp e c tru m

24 19 16 14 14 12. 9 8 7 4
f(cycle/s)= 1x10 1x10 1x10 8x10' 4x10 1x10 1x10 1x10 1x10 1x10

V/ i t I
7 ray x ray ultraviolet visible infrared m icrow ave | radar television radio

T T T T f t T T T
= 1x10 5 1x10"' 100 500 1x10 3 1 1 10 1000
run run nm nm cm cm m m m

1
violet blue green yellowj orange red

T 455 490 580 600 620 T

X= 390 770
1 .. ,
run
...
nm
<"
IRE 6.10 A p p ro x im a te fr e q u e n c ie s a n d w a v e le n g th s o f e le c tro m a g n e tic sp e c tru m .
W hen gases o r vap o rs o f ch em ical sub stan ces are heated , atom s o f the
color X(nm) E (k ca l/m o l) su b stan ce ab sorb energy. A fter an atom absorbs a q u antum (a p ack ag e) o f
en erg y , it is said to be in an e x c ite d s ta te . W hen an ex c ite d ele c tro n re ­
- » red 6 5 6 .3 4 3 .6 tu rn s to its n o rm al (g r o u n d ) state, lig h t is em itted. I f a ray o f this lig h t is
p assed th ro u g h a prism , a lin e s p e c tr u m is pro d u ced . L in e sp e ctru m c o n ­
sists o f a lim ited n u m b er o f co lo red lines, each o f w h ich co rresp o n d s to a
—» gYeen 48 6 .1 ~^58.8 d iffe re n t w a velength o f light. T he line spectrum o f each elem en t is unique.
-> blue 4 3 4 .0 65 .9 F o r exam ple, w hen electric cu rren t flow s in the h y d ro g e n tube, red lig h t is
- » v io le t 4 1 0 .1 6 9 .7 em itted b y h y d ro g en atom s. I f this lig h t is passed th ro u g h a p rism , the line
—» u ltraviolet ato m ic spectrum o f h y d ro g en is obtained as sh o w n in F ig u re 6.11. W e can
d ed u ce th a t h y d ro g e n atom can em it lig h t only at sp ecific w av elen g th s o r
1 /
energies. W hy ? T he spectrum o f hydrogen depends o n the structure o f the
FIGURE 6.11 H y d r o g e n h y d ro g en atom .

f,Z T fZ Z lT J Z i 6.3.3 THE BOHR MODEL OF ATOM

c o r r e s p o n d s to a s in g le In 1913, N ie ls B o h r (1 8 8 5 -1 9 6 2 ), a D a n ish P h y sic ist, p ro p o sed a the-
w a velength. T he light em it- o ry fo r electro n ic structure o f hydrogen atom that ex p lain ed the lin e spectrum
te d b y h y d r o g e n c o n s is ts 0 f h y d ro g en atom . T h e hyd ro g en atom contains one electron and one p roton in
o f light o f s p e c ific e n e r - • Г a .u г i,
• its n u cleu s. B o h r s theory includes the fo llo w in g assu m p tio n s :
 Atomic Structure and Chemical Periodicity 209

1. T he electron o f h yd ro g e n a to m c o u ld b e fo u n d o n ly in ce rta in fi x e d
o r b its o r en erg y le v els o r sh e lls. T h e se o rb its are arran g ed c o n ce n tric ally
aro u n d th e nu cleu s, and show n by e ith er the letters K, L , M , N ... o r n u m b ers
1, 2, 3, 4 , .... n. T h e se n u m b ers are referred to as the p r in c ip le q u a n tu m
-21
2.18 x 10 n u m b ers.
kJ/e 2. T he electron in a given o rb it has a d efin ite qu a n tity o f energy th a t can
be calculated by the fo rm u la :
-22
E„ = - 1312-4 kJ/mol e 5.21 x 10
E„ = • kcal/e n = 1 , 2 , 3 ...... (number o f orbit)

I f w e co n sider 1 m ol o f electrons th eir en erg y w ill b e :

-22
5.21 x 10 6.02 x 10 e 313.6
E„ = ■kcal/e x or E„ = k c a l/m o le
n 1 mol

So w e can determ ine the energies o f electrons in kcal/m ol in the allow ed

en erg y lev els as follow s.
1807 313.6
Es= = -1 2 .5 kcal/mol
D a lto n m o d el n=5'

,n = 4 E 4 = -1 1 1 ^ . = -1 9 .6 kcal/mol
P’ p* 42
n=3 313.6
E ,= = - 34.8 kcal/mol
32
e~ * e~ n=2
313.6
E, = - = - 78.4 kcal/mol
n=1
p‘
T h o m s o n m o d el Ei = 1 I M = -313.6 kcal /mol

T h e first lev el ( n = l) clo sest to the n u cleu s is called th e gro u n d state, o r

th e g round level. T he electron in this level has the sm allest energy, therefore it
has the g reatest stability. T he stability o f electro n decreases fo r the h ig h e r le v ­
els (n = 2, 3, 4 ..), and th ese arc called ex cited sta tes, o r ex cite d lev els.
T h e negative sign in equation, E n = -313.6/n2, is n o thing m ore th an arb i­
trary convention. T h e energy o f a free electron (electron infinitely far from the
n u c le u s) is a rb itrarily assigned a v alu e o f zero. A s the e lec tro n gets clo ser to
1911
the n u cleus its energy decreases and E n b ecom es la rg e r in ab so lu te v alu e, but
R u th e rfo rd M odel
also m o re negative.
3. A s long as an electron rem ains in a given o rb it its energy rem ains con­
sta n t a n d it does n o t em it energy. W hen an electro n falls from a h ig h e r en erg y
level to a low er one, the atom em its a quantum o f radiation w h o se en erg y (hf)
is equal to the difference in the energy o f tw o states.
AE = E r - Ej = h f = h ^ - | (i and f indicate initial and final states of electron)

1913 C o n v ersely , rad iatio n e n erg y is ab so rb ed w h en ele c tro n s ju m p from a

B o h r m o d el lo w e r en ergy orbit to a h ig h er one. In this case the sign o f Д Е is p o sitive in d i­
cating th at the process is energy consum ing o r endotherm ic.
B o h r show ed that each electron transition fr o m a h ig h er energy o rb it to a
' 210 Chapter 6

Lower o n e p ro d u c e s a line in the sp ectrum . T h e fo llo w in g ex am p les illustrate

the point.

EXAMPLE 6 . 1 8 C a lc u la tio n s A b o u t E le c tr o n T r a n sitio n s in H y d r o g e n A to m

Problem .'Calculate each of the following for the electron transition in which an electron in a hydrogen atom
drops from the level n=4 to the level n=2.
a) Energy of photon emitted. b) The frequency of the photon.
c) Wavelength of the photon. d) The region of this spectral line in electromagnetic spectrum,
e) Is there this color of line in the spectrum of hydrogen ? (Consult Figures 6.10 and 6.11)
Solution :
a) The energy of photon emitted or absorbed depends on the energy difference between its final and initial orbits.

AE = E r E| = E 2- E 4= ^ 1 M - : l lJ A = -78.4 - (-19.6) = -58.8 kcal/mol

2 4
The negative sign here does not have a mathematical meaning. It indicates that atom has lost the energy (exother­
mic process). There is no need to consider this negative sign in calculating frequency or wavelength.

b) AE = hf => f = — = ------58.8 kcal/mol = 6.164 x 10^ 1/s

^ 9.54 x 10 kcal.s/mol
s
c) = -----3 -l() m/s---- = 4.867 x 10’ m s 487 nm
f м
6.164 x 10 1/s
d) From Figure 6.11 we sec that the light with frequencies between 4 x 1014 and 8 x 10 14 (or wavelengths be­
tween 400 and 700 nm) is in the visible region, and this light has blue-green color.
c) We observe a spectral line in the emission spectrum of hydrogen atom. Actually the electron transitions from
higher energy levels to the level n=2 produce spectral lines in the visible region. See Figure 6.12.

~ h

FIGURE 6.12 E lectro n tra n sitio n s b e tw e e n tw o le v e ls o f h y d ro g e n a to m p r o d u c e a s p e c tr a l line in th e s p e c ­

trum. A n e lec tro n transition from a h ig h e r-e n e rg y le v e l to th e n=2 le v e l g iv e s rise s p e c tr a l lines in th e visible re ­
gion.
N ote : We have solved the problem in part (a) for one mole of electrons transferred from n=4 to n=2. The prob­
lem may be solved for one electron transition only. In that case we should use the equation
-22

E „= - 5/21 x 10 kcal so E 2= -1.30 x lO'22kcal and E 4= -3.26 x ю ’2 kcal

n2
 Atomic Structure and Chemical Periodicity 211

and, ДЕ = E 2 - E 4 = (-1.30 x 10"22) - (-3.26 x 10'23) = 9.74 x 10' 23 kcal. The frequency and wavelength could be
calculated by using the formula ДЕ = hf = h — • The value of h should be taken as h = 1.58 x 10'37 kcal.s.

EXER C ISE 6.24 What arc die frequency and wavelength in A° o f a photon emitted during a transition
from the n=5 state to the n=3 state in the hydrogen atom? f = 2 . 3 4 x / 0 1 4 l is, X = l . 2 8 x l 0 ' 6m = l 2 8 0 0 Л 0

E X E R C IS E 6.25 A line in the spectrum of atomic hydrogen has a wavelength o f 4.34 x 1()'7 m. The
electron transition from which level to which one gives rise to this spectral line in hydrogen atom ? S -* 2

EXERCISE 6.26 Calculate the frequency of the radiation that is necessary to jump (or promote) one elec­
tron of hydrogen atom from the n=2 level to the n=3 level. In which region of electromagnetic spectrum docs
this radiation lie ? W hat color is it ? 4 . S 7 x K ) 14 1 /s, visibl e re gi on, r e d

6.4 WAVE MECHANICS AND

MODERN ATOMIC THEORY
6.4.1 S H O R T C O M IN G S O F B O H R 'S A T O M IC MODEL
A lth o u g h B ohr's theory is highly su ccessfu l in e x p la in in g the em issio n
sp ectru m o f h y d ro g e n atom , it could n o t ex p la in the ap p ea ra n ce o f the extra
lines in the h y d ro g en atom placed in a m ag n etic field. It also fails to ex p lain
the sp ectra o f m o re co m p lex atom s such as th o se o f h eliu m , lith iu m , ... A n ­
o th e r p ro b lem w ith B o h r's m o d el is the assu m p tio n o f a w e ll-d e fin e d o rb it
a b o u t w h ic h e le c tro n ro tates. A c c o rd in g to H e is e n b e r g 's u n c e r ta in ity
p rin cip le it is im possible to define a certain orbit for electrons b ecause the e x ­
act p o sitio n and v elo city o f an ob ject as sm all as the electron can n o t be d e te r­
m ined sim ultaneously.
If w e w ant to see an object, the object m u st be cither a source o f radiation
o r reflect the radiation w e sent onto it. B ohr said that electrons do not em it any
radiation in a given orbit, thus they are n o t source o f light. So w e can only see
electrons by m eans o f the light reflected by them . Since the size electron is e x ­
trem ely sm all, w e have to use a radiation w ith an ex trem ely short w av elen g th
to lo cate an electron. A rad iatio n w ith short w av ele n g th has h ig h frequency
FIGURE 6.13 (a) A long and high energy. W hen it strikes the electro n , the im p act causes the direction
wave radiation cannot be o f m otion and speed o f electron to change. T h u s w e can n o t see the ex act path
used to determine the lo­
o f electron. Instead w e can estim ate t h e r e g i o n o r v o l u m e i n w h i c h t h e p r o b a ­
cation of electron in an
b i l i t y o f f i n d i n g a n e l e c t r o n i s t h e g r e a t e s t . T h is region is called orb ita l. A n
atom, (b) A short wave ra­
diation causes the place o r b ita l c a n b e c o n s id e r e d a s a p ic tu r e o f th e p r o b a b ility o f f i n d i n g a n e le c tr o n
of electron to change. a t e v e r y p o i n t in s p a c e .
Therefore it is impossible 6.4.2 M O D E R N A T O M IC T H E O R Y
to determine the exact or­ In 1924 L ois de B r o g lie p ro p o se d th at e le c tro n s o r o th e r p a rtic le s
bit of the electron.
have w ave properties. T h e ex act n ature o f th ese "electron w aves" w as u n clear
but de B ro g lie w as able to p resen t a m a th e m a tica l p ro o f fo r his idea. B o h r
T h e te rm " o r b i t a l " is
m odel did n o t take into account the w ave aspect o f the electron. C onsequently,
u se d to d e fin e the d istrib u ­
tio n o f e le c tro n d e n sity in B ohr's m o d el w as ab ondoned and a new ato m ic m odel w as pro p o sed in the
sp ace. It h a s th ree d im e n ­ lig h t o f the q u a n tu m m e c h a n ic s o r w ave m ech a n ics. B o t h B o h r ' s t h e o r y
sions and is d iffe re n t from a n d q u a n tu m m e c h a n ic s s h o w e d th a t th e e n e r g y o f e le c tr o n in h y d r o g e n a to m
th e o rb it w h ic h is u se d in is q u a n t i z e d . H o w e v e r , t h e y d i f f e r i n t h e i r d e s c r i p t i o n o f t h e e l e c t r o n 's b e h a v ­
c o n n e c tio n w ith B o h r m o ­
i o r w i t h r e s p e c t to t h e n u c le u s .
d e l.
212 Chapter 6

6.4.3 QUANTUM NUMBERS

W ave m ech an ics tells us th at fo u r q u antum n u m b ers are req u ired to d e ­
scribe the b e h a v io r o f electrons in h y d ro g e n atom o r o th e r atom s. T h e y are
called 1) the p rin cip le quantum n u m ber 2 ) the seco n d a ry q u a n tu m nu m ­
b e r 3) the m agnetic quantum num ber 4) spin quantum num ber.
1) T he p r in cip le q u a n tu m n u m b er (n) : It d e te rm in e s the en erg y
level o r sh ell o f the electron. It can have any integral value greater than zero.
n = l , 2, 3... “
F o r h y d ro g e n atom , the p rin cip le q u an tu m n u m b e r is the sam e as the
n u m b e r o f o rb it in B o h r’s m odel. The la rg er the va lue o f n, the g re a te r the
energy o f the orbital a.iui the fa rth e r the electron is fr o m the nucleus.
2 ) T h e se c o n d a r y q u a n tu m n u m b e r , or a z im u th a l q u a n tu m
n u m b e r (/) : I t d ivides the sh ells into su b sh ells o r sub levels. T he n u m ber
o f su b sh ells in a p rin c ip a l sh ell is equal to the value o fn . E ach su bshell has
a seco n d ary quantum n u m b e r th at has integral valu es from 0 to (n-1). T here
is o n ly o n e su b sh ell (/= 0 ) in the first shell (n = l) , th ere are tw o sub sh ells
(/= 0 , /= 1) in the second shell (n= 2 ), and three subshells (/= 0 , 1= 1 , 1= 2 ) in the
th ird shell (n=3). A letter code is norm ally used to denote the subshells.

r / 0 1 2 3 4 ^ Г л
subshell s p d f g h i
V I.,.-.VI J
In m u ltielectron atom s the energies o f the electrons in the orbitals w ithin
a shell increase in the follow ing order.
s electrons < p electrons < d electrons < f electrons.

shell mneiple quantum secondary quantum number orbitals

num bcr(n) /=(), ], 2 ...(n- 1)
3s
0 is
(b) 0 2s
T Or
-I'
FIGURE 6.14 (a) Plot 0 3s
of s orbitals. Although an M I Щ 3p
electron can be found 3d
V.
anywhere,it spends most
of its time quite close to 3) T h e m a g n e tic q u a n tu m n u m b er (m p : I t d iv id e s su b sh e lls into
the nucleus the probabili­
in d ivid u a l orb ita ls. F o r each valu e o f /, th ere are (2 /+ I) in tegral valu es o f m ;
ty of finding an electron
with a sphere surround­
from -/ to + / in clu ding zero. F o r ex am p le if 1=0 (s orb ital), th en , m p O (only
ing the nucleus is great­ one type o f s orbital). If l= \ (p orbital), there are [(2x1) + 1)] or 3 values o f m /
est. But it falls off rapidly g iv en by -1, 0, and +1. So there are three types of.p o rb itals w h ich are called
as the distance from the p x, p y, and p z. S im ilarly, if 1=2 (d orb ital), th ere [(2x2) +1)] o r 5 d iffe re n t
nucleus increases, (b) v a lu e s o f n q ( - 2 , -1, 0, +1, +2). T h u s there are 5 types o f o rb ita ls (d xy, d xz,
All s orbitals are spheri­
d y z , d x 2 . y 2 Clz2) .
cal in shape but their siz­
es increase as the princi­ The total num ber o f orbitals in the nth p rin c ip a l shell is n2. T he first shell
p le quantum num ber (n= 1) has l 2 o r 1 o rbital w hich is called Is, the second sh ell (n= 2) has 2 2= 4
increases. o rb itals w h ich are 2s, 2 p x, 2 p y, 2 p z, th e th ird energy le v e l (n= 3) has 3 2 o r 9
 Atomic Structure and Chemical Periodicity 213

o rb itals (3s, 3px, 3py, 3pz, 3dxy, 3dx z, 3dyz, 3d x2.y2 and 3dz2), and th e fo u rth
en erg y le v e l lia s 4 2 o r 16 orbitals (one s, three p, five d, and se v en f orbitals)
See F ig u res 6.14 and 6.15.

FIGURE 6.15 The different orientations of the three equivalent p orbitals.

Except for their orientations the three p orbitals in a given shell are identical in
shape and energy.
4) T h e s p in q u a n t u m n u m b e r (m s) : It re fers to the tw o spirting m o ­
tions o f electron one clockw ise a n d the o th er co u nter clockw ise. It has the v a l­
FIGURE 6 . 1 6 T h e u es o f + 1 Д o r -1/2 one fo r clockw ise and the o th e r fo r c o u n te r clockw ise. See
clockwise and counter­
F ig u re 6.16. E a ch o rb ital can c o n tain a m ax im u m o f tw o e le ctro n s th at have
clockwise spins of an
electron. The vertical ar­
identical n, I, and m/ values but differ in theirs m s values.
rows are used to denote T h e relatio n b etw een q u antum n u m b ers and ato m ic o rb itals is su m m a r­
the two directions of spin. ized in T ab le 6.2.

T A B L E 6.2 S u m m a ry o f q u a n tu m n u m b ers
~\
sh ell n / m/ n u m b er o f ms m ax im u m n u m b er o f e le c ­
( 1 . 2 , ..ii) l l , 2 ,..( n - l) l ( - / .. . 0 ...+ /) o rb ita ls (n 2) (+ 1 / 2 , - 1 / 2 ) trons in e a c h sh e ll( 2 n 2 )
К 1 0 0 (Is) + 1/2
1 1 \ 2
0 0 (Is) - 1/2 1 J
2 0 0 ( 2 s) + 1/ 2 . - 1 / 2 2

L 2 1 -1 ( 2 Px) + 1/ 2 , - 1/2
4
2 1 0 ( 2 P y) + 1/ 2 , - 1/2 2 } «
2 1 1 ( 2 p z) + 1/ 2 , - 1/2 2

3 0 0 (3s) 2

M 3 J -1, 0, +1 (3p) ± 1 / 2 for each

9 6 I 18
3 2 (-2. -1, 0, +1, +2) (3d) value o f m/ 10 J
(3dxv,3 d x/,3 d vz,3dx2.v2,3d/ 2)
4 0 0 (4s) 2

N 4 1 - 1 ,0 , +1 (4p) ± 1 / 2 for each

16
4 2 - 2 .- 1 , 0, + 1, +2 (4d) value o f m / to } 32
4 3 -3, -2, -1, 0, +1, +2, +3 (4f) 14
V : - ?!

E X A M P L E 6.19 P r e d i c t i n g T y p e s a n d N u m b e r s o f O r b i t a l s
Problem: Indicate the number of subshells (or kind of orbitals), the number of orbitals and the values of n, /,
ni; for the orbitals in the level n=5 or О shell.
214 Chapter 6

Solution : Each shell or principle level o f quantum number n contains n subshclls or sublevels. So there arc
five subshells in the fifth energy level which are s, p, d, f, g subshells, having the secondary quantum numbers
0, 1, 2, 3, 4. The total number o f orbitals in a given shell is n2. Therefore the total number o f orbitals is 52 or
25. There is one 5s orbital (n = 5 ,1=0, m/ =0), three 5p orbitals (n=5, /=1 and m/ =-1, 0, 1), five 5d orbitals (n=5,
1=2 and m /= -2, -1 ,0 , 1, 2), seven 5f orbitals (n = 5 ,1=3, m/= -3, -2, -1 ,0 , 1 ,2 , 3) and nine 5g orbitals (n = 5 ,1=4
and m /= -4, -3, -2, -1 ,0 , 1 ,2 , 3 ,4 )

EXERCISE 6.27 Which ones of the following atomic orbitals arc unacceptable ? Ip, 2s, 2d, 4p, 6 s, 3f

\ 6.5 ELECTRON C O N F IG U R A T IO N
H aving d iscussed the shape and the n u m b e r o f atom ic o rb itals, let us see
h o w electro n s are d istrubuted am ong the v ario u s orbitals. The a rra n g em en t o f
e le c tro n s in th e o rb ita ls o f an a to m is ca lle d the e le c tr o n c o n f ig u r a tio n o f
th e atom . T h e e lec tro n co n fig u ratio n s o f atom s in th e ir g ro u n d states can be
T h e e n e rg y o f an o rb ita l
predicted u sin g the follow ing rules.
in c re a s e s w ith in c re a s in g
its (n+l ) v a lu e s . F o r the ] R u le I : E le ctro n s in an atom o ccu p y the lo w e st p o ssib le en erg y levels
sa m e (n -ь/) v a lu e s th e o r­ or orbitals. A s w e have stated before the energy o f an orbital is determ ined by
b ita l w ith sm a lle r v a lu e o f the principle quantum n u m b e r o f the o rbital fo r hyd ro g en atom . B ut fo r m u lti­
n h a s lo w e r e nergy. electron atom s the energy o rd er o f orbitals is d e ten n in e d by the principle q u a n ­
tum n u m b e r and seco n d ary quantum num ber. T h e en erg y o f o rb itals is a ffect­
ed b y the m u tu al rep u lsio n o f electrons in m u lti-electro n atom s. T h erefo re the
o rd er o f in creasing orbital energy fo r m u lti-electron atom s m ay b e determ ined
b y u sin g F ig u re s 6.17 and 6.18.
[7
Number of
Elements
Is
» 1J
2 s 2p
j ft ! )
3s 3p 3d
С | П? r \
4s 4p 4d 4 f
? ! P i A
5s 5p 5d 5f
r ? I
6 s 6p 6d 6 f
P ft : i C l
7s 7p 7d 7f

FIGURE 6.18 T h e o rd e r in w hich

a to m ic o rb ita ls a re fille d in m u lti­
elec tro n atom . W e sta rt with th e 1s or­
bita l arid m o v e in th e d irection o f c o n ­
n e c tin g lines. T h u s th e o rd e r g o e s a s
follow s :
1s < 2 s < 2 p < 3 s < 3 p < 4 s < 3 d < 4 p ...
 Atomic Structure and Chemical Periodicity 215

R u le I I : E a c h a tom ic o rb ita l can be o ccu p ied b y m a xim u m o f tw o elec­

tro n s. A cco rd in g to the P au li E x clu sio n P rin cip le, no tw o e le ctro n s in the
sam e atom can have the sam e set o f fo u r quantum num bers. T h e tw o electrons
in the sam e orbital have different spins, (o r spin quantum num bers)
N o w le t use th ese rules to w rite the e le ctro n co n fig u ra tio n s o f th e e le ­
m en ts iH , гН е, 3Li, 4B e, and 5B
H y d ro g en atom (Z = l) has one electron. T h is electro n w ill be in the lo w ­
est energetic orbital w hich is Is. So its electron co n figuration is :
H : Is1 (read one s one).

1 in d icates the n u m b er o f e lectro n s in the o rb ita l

H: I s 1 in d icates the k in d o f su b le v el o r o rb ita l o r se c o n d ary q u a n tu m n u m b e r
Q —» e m p ty o r b ita l I in d icates the p rin cip le q u a n tu m n u m b e r o r shell.
© —» h a lf-fu ll o rb ita l
(JJ )—♦ c o m p le te ly full
T h e electro n con fig u ratio n s can b e represen ted also by o rbital d iag ram s
o rbital in w hich an orbital is represented by a circu lar box (in som e b o o k s b y a square
box), and electrons by vertical arrow s.
H : (J) (T he ch o ice o f u p w ard arrow is c o m p le te ly a rbitrary)

F o r helium (Z = 2) the electron configuration is :

H e: I s 2 (read "one s tw o", n o t "one s squared"). O r :
H : ©
H e: @ (orbital diagram notation)
He
'■(0 ) T h e tw o electrons in the Is o rb ital fo r helium atom have d iffere n t spins.
Li ® 0O O O T h e o p p o site d irectio n s o f arrow s in the o rb ital rem in d s the P au li E x c lu sio n
Be
principle. A cco rd in g to the second rule Is orbital is no w full and it can n o t ac­
:@ © О О О com odate m o re than tw o electrons.
В :
© О ФОО F ig u re 6.18 in d icates th at the third electro n o f L ith iu m atom (Z = 3) w ill
Is 2 s 2 p go in the 2 s orbital
3Li : 1s 22 s ' o r 3L i : @ © О О О
Is 2 s 2 p
S im ila rly :
4B e : 1s 22 s 2 o r 4B e : @ @ О О О md

5B : l s ^ s V o r 5B : ® @ ФОО
1 s 2 s 2 p

R u le I I I : T he electro n co n fig u ratio n o f C (Z = 6 ) is l s 22 s 22 p 2. H ere w e

face w ith a d ifficu lty in p lacin g tw o electro n s am o n g three p o rb itals as fo l­
lo w s @ 00 or
ООО or
ФОО
2 p x2 p y2 p z 2 p x2 p y2 p z 2 p x 2 p y2 p z
W hich o n e is the correct electron co n fig u ratio n o f the С atom ? T h e an ­
sw er is p ro v id ed by H u n d 's ru le .* H a n d 's rule sta tes th a t electro n s are d is­
trib u te d a m o n g the o rb ita ls o f equal en ergy in a w ay th a t g ive s the g re a test
num b er o f u n p a ired electrons o f the sam e spins (o r parallel spins). O r w e can
sim p ly say that a given set o f p, o r d o r f orbitals is sin g ly o ccu p ied by e le c ­
trons rather than in pairs. T hus the correct electron co n fig u ratio n o f the carbon
atom i s :
* Frederick Hand : A German Physicist
 216 Chapter 6

E le c tro n s h a v in g o p p o ­ eC:@ @ ©CDO or 6C : l s 22 s 22 p ' 2 p'y 2 p ,

s ite sp in s in th e sa m e Is 2 s 2 p
o rb ita l a re s a id to be
w e can und erstand w hy this co n fig u ratio n is p referred by saying that the
p a i r e d . T h e atom s h a v ­
electro n s in the sam e orbital repel each o th e r and th ere fo re electro n s occupy
in g u n p a ire d e le c tro n s
a re p a r a m a g n e tic ( a t ­ the orbitals as m any single electrons as possible in the atom .
trac te d b y m ag n e ts). N ow w e can continue to w rite the electron configurations o f elem ents

7N : © ©Ф© or 7N : ls22s22p3
Is 2 s 2 p
80 : @Ф© sO : ls22s22p4
Is 2 s Zv
9F : @ @@ф 9O : ls22s22p;
Is 2 s 2 p
ioN e : © Ф ioN e :: ls22s22p*
Is 2p
2 s
T h e ato m s th at have co m p le te ly full o r co m letely h a lf-fu ll o rb itals are
m ore stab le b ecause o f the sy m m etrical electro n d istrib u tio n o f th ese atom s.
H e : I s 2, and N e : l s 22s 22p 6 have com p letely full o rb itals th erefore they have
the greatest stability. On the o th er hand, N : l s 22s 22p 3 contains com pletely full
( I s and 2s) and co m p letely h alf-full (p x, py, p z) o rb itals. N itro g e n h a s also
greater stability than the other atom s.

E X A M P L E 6.20 W r itin g E le c tr o n C o n fig u r a tio n s o f A to m s

Problem : Write the electron configuration of each of the following atoms. Indicate the number of unpaired
electrons in each atom. a fn N a b) 15P с) гоСа d) 30Z 11 0)531
Solution
a) u Na : ls 22s 22p 63 s l 4 : (one unpaired electron)
b) 15P : ls 22s 22p 63s 23p 3 (three unpaired electrons, one electron in each p orbital)
c) 2oCa : ls 22s 22p 63s 23p 64s 2 (no unpaired electrons)
d) 53I : ls 22s 22p 63s23p 64s 23d 104p 65s 24 d l05p5 (one unpaired electron)

EXERCISE 6.28 Wriie the electron configurations of the following elements in both subshell notation
and orbital diagram notation. a )C I(Z = !7 ) b )K (Z = lh ) c ).\s (Z = 3 3 ) d) Rn (Z= 86)

R u le IV : I f t h e e l e c t r o n c o n f i g u r a t i o n o f a n e l e m e n t e n d s w i t h e i t h e r
n s 2 (n - 1) d 4 or n s 2 (n - 1 ) d 9, t h e c o n f i g u r a t i o n i s c h a n g e d t o n s 1 (n - 1 ) d 5
o r n s 1 (n - 1 ) d 10 r e s p e c t i v e l y . T h is ch a n g e o c c u rs b e c a u se the e x iste n c e o f
c o m p le te ly h a lf-filled (d 5) o r co m p letely filled (d 10) d o rb itals in atom gives
greater stability to the atom .L ook at the follow ing exam p les to u n d erstan d how
th e rule is applied.
2 4 C r: @ @ @ @ @ @ @ ф ф ф ф ф (expected)
T h e e x is te n c e o f c o m p le ­ Is 2s 2p 3s 3p 4s 3d
tely h a lf-fille d (p 3 ,d 5 , f7 ) 24C r : @ @ @ @ @ @ ф ф ф ф ф ф (R eal)
and c o m p le te ly filled o rb i­ Is 2s 2p 3s 3p 4s 3d
tals (s 2 ,p 6 , d 1 0 , f 1 4 ) g iv es T h e sa m e k in d o f electro n tran sfers o ccurs in the e lem en ts 42M 0 and
e x tra sta b ility to atom s. 74W.
 Atomic Structure and Chemical Periodicity 217

29Cu : © © @ @ © © © @ © @ © ф (expected)
Is 2s 2p 3s 3p 4s 3d
29CU : © © © @ @ @ @ @ @ ф @ © @ © @ (R eal)
Is 2s 2p 3s 3p 4s 3d
T he electro n tran sfer front s 2 to d 9 o rb itals are also o b se rv ed in th e e le ­
m ents 47A g and 79AU.
So far w e have discu ssed the electro n co n fig u ratio n o f th e g ro u n d state
o f atom s. W hen an atom gains energy its electrons ju m p to h ig h e r energy le v ­
els than th eir original energy levels. S uch a co nfiguration o f an atom is called
its excited state electron configuration. F o r exam ple :
G round - state E xcited state
iH : I s 1 iH : З р 1
6C : l s 22 s 22p 2 6C : l s ^ s ^ p ^ s 1
U n less it is stated w e w ill c o n sid e r the gro u n d state ele c tro n co n fig u ra ­
tio n o f atom s. T he ground state e le ctro n c o n fig u ra tio n s o f the ele m en ts are
given in T ab le 6.3.
T A B L E 6.3 T h e E lectro n C o n fig u ra tio n s o f the E lem e n ts

A to m ic
Element Num ber Bohr Model Wave M echanical Model

Hydrogen (H) 1 1 je 1s 1
Ф'
H elium (He) 2
Ф 2)e 1s2
L ithium (Li) 3 й 2)e 1 )e 1s22s1
B eryllium (Be) 4
Ф 2)e 2 )e 1s22s2
Boron (B) 5
Ё 2)e 3 je 1s22s22p1
Carbon (C) 6
* 2)e 4 je 1s22s22p2(dr 2pJ 2pJ)
N itrogen (N) 7 2)e 5 je 1s2 2s2 2p3 (or 2pJ 2pJ 2p^)
m
Oxygen (O) 8 2)e 6^e 1s2 2s2 2p4 (or 2p2 2pJ 2p ’)
m
9p 1s2 2s22p5
Fluorine (F) 9
IP 2)e 7)e
Neon (Ne) 10 2)e в \е 1s22s22p6

Sodium (Na) 11 2 je в)е 1'j e 1s22 s 22p6 3 s1

Ш

M agnesium (Mg) 12 8 je 2^e 1s2 2s2 2p6 3s2

Ш 2)e
A lum inum (Al) 13 2)e в)е з]е 1s2 2s2 2p6 3s23 p 1
Ш
S ilicon (Si) 14 2)e 8 je 4)e 1s2 2s2 2p6 3s2 3p2 (or 3pJ 3pJ)
w
P hosphorus (P) 15 ф 2)e 8^e $ \e 1 s2 2s2 2p6 3s2 3p3 (or 3p I 3pJ 3p])

8 je 6^e 1s2 2s2 2p6 3s2 3p4 (or 3p2 3pJ 3pi) v
S u lfu r (S) 16
® 2)e
MjL 8^e Z^e Ts2 2s2 2p6 3s2 3p5
C hlorine (Cl) 17 2)e
8^e в)е 1s22s22p6 3s2 3p6
Argon (Ar) 18
m 2)e
P otassium (K) 19 2)e 8^e 8^e 1^e 1s22s22p63s23p64 s1
m
C alcium (Ca) 20 2)e 8^e 8^e 2^e 1s22s22p63s23p64s2 ,
Ш
218 Chapter 6

E X A M P L E /6 .2 1 W r itin g E le c tr o n C o n fig u r a tio n s o f A to m s a n d I o n s

Problem : w riie-thc configuration o f the following species.
a) Ti (Z=22) b) Se (Z=34) c) Mo (Z=42) d) Ca2+ (Z=20) e) P3' (Z=15)
Solution :
a) 22T i : ls 22s 22p 63s23p 64s 23d 2 or we may rearrange it by grouping the subshells o f the same shell as follows.
22T i : ls 22s 22p 63s 23p 63d 24 s 2
b) 34Se : ls 22s 22p 63s 23p 64s 23d 104p 4 or ls 22s 22p 63s 23p 63d 104s 24p 4
c) 42Mo : ls 22s 22p 63s23p 64s 23d 104p 65 s 14d 5 (Recall rule V)
d) Ca2+ has 20 protons but 18 electrons (2+ charge means the loss of two electrons relative to its neutral state).
The electrons that are removed from the atom are the electrons in the outermost energy level which is 4s in case
of Ca. So the electron configuration of Ca2+ is : 2oCa2+ : ls 22s 22p 63s23p 6
e) 15P 3 has 15 protons but (15+3) or 18 electrons. The electron configuration is : 15P3' = ls 22s 22p 63s 23p 6

E X A M P L E 6.22 C a lc u la tio n s B a se d on E le c tr o n C o n fig u r a tio n s

Problem : T he electron configuration o f a neutral atom having 42 neutrons in its nucleus ends w ith 4 p 3.
W hat is the m ass num ber o f the atom ? Could you identify it ?
Solution : E lectron configuration -» ? num ber o f electrons —> ? num ber o f protons —> ? m ass num ber
Since the electron configuration o f the atom ends w ith 4 p 3 then, all the orbitals that have less energy then 4p
should be full o f electrons. O r the electron configuration o f the atom m ust be : X : ls5 2 s22p63s23p64 s23 d 104 p 3
N eutral X atom has (2+2+6+2+6+2+10+3) or 33 electrons and therefore 33 protons. A = p + n = 33 + 42 = 75
From the periodic table, w e see that the clem ent is arsenic.

E X E R C ISE 6 . 2 9 W hat is the atom ic num ber o f the clem en t w hose last tw o electrons are located in 3d
o rb ita ls ? 22

E X ER C ISE 6 . 3 0 Each o f the species X 2+< Y3‘, and R has the sam e electron config u ratio n en ding with
2 p 6. D eterm ine the atom ic num ber o f each o f these elem ents. 12 , 7, 10

E X ER C ISE 6 .3 1 T he electron configuration o f a m onoatom ic ion, X ' ends w ith 4 p 6. If the atom ic n um ­
ber o f X is 34 w hat is the charge o f the ion ? 2-
1--------------------------------------------------------------------------------------------------
E X E R C ISE 6 . 3 2 T he electron configuration o f X4' ends w ith 3p6. If the num bers o f pro to n s and neu ­
trons o f X are equal, find the atom ic m ass num ber o f X. 2S
—
___________________________
E X A M P L E 6 . 2 3 C a l c u l a t i o n s B a s e d o n E le c tr o n C o n f ig u r a tio n s
Problem : T he m olecular w eight o f X 20 3 is 160 g. If X atom has 6 electrons- in 3d orbitals, how m any neu ­
trons does it have ?
Solution : A tom ic w eight o f X = (160 - 48) / 2 = 56. T he atom ic w eight equals the m ass num ber, A = 56.
From the electron configuration, the num ber o f protons and electrons can b e calculated;
X : 1s22s22 p 63s23p64s23d6,: then e ” = p = 26 ; A = p+n -> 56 = 26+n -+ n = 30

6.6 PERIODIC TABLE

E arly in th e n in eteen th cen tu ry , c h em ist b eg an to und erstan d ' that there
are sim ilarities in the chem ical properties o f elem ents, and suggest a system atic
classification o f elem ents based on th eir properties. T he first attem pt w as m ade
 Atom ic Structure and Chemical Periodicity 219

by J .W .D o b e r e in e r in 1829. H e arranged the ele m en ts in o rd e r o f in c re a s­

ing atom ic w eights. B ut he w as n o t s u c c e sfu l/b e c a u se the ato m ic w eig h ts o f
elem ents w ere not determ ined exactly, and m any o f the elem ents w ere n o t d is­
covered yet.
In 1869 the R u ssian ch em ist D m itri M e n d e leev , and L o th a r M ey er
(a G erm an chem ist), w o rk in g in d ep en d en tly , show ed th at the p ro p e rties o f
elem en ts are perio d ic functions (properties rec u r at d efinite in terv als) o f th eir
atom ic w eights. H ow ever this kind o f arrangem ent created exceptions in a few
cases such as К (39.948 am u) and A r (39.102 am u) or I (1 2 6 .9 0 4 am u) and
Т е (1 2 7 .6 0 am u). I f the ele m en ts w ere arran g ed a c co rd in g to th e ir ato m ic
w eights this w ould put argon in place o f potassium o r Т е in place o f I.
In 1913 A B ritish P h y sicist H en ry M o seley proposed th at the p ro p e r­
ties o f elem ents w ere actually periodic functions o f th eir atom ic num bers rather
than their atom ic w e ig h t^ T h u s the modern periodic table is an arrangement o f
atoms in increasing order o f their atomic numbers that collects atoms with sim ­
ilar chemical properties in a vertical colum n/See the periodic table printed on
the in sid e front cover. The horizontal colum ns are called p eriod s or r o w ^ f
T h ere are seven periods. T he first period has tw o elem ents hydrogen and h e li­
um . T h e second period consists o f 8 elem ents from lithium to neon. T h e third
p erio d also co n tain s 8 elem en ts b e g in n in g w ith sodium and 4e n d in g w ith a r­
gon. T h e fourth and fifth p eriods co ntain 18 elem en ts each. In the six th and
se v e n th p erio d s, tw o series o f elem en ts, lan th a n id e series and aelined series,
are set below the m ain body o f the periodic table to avoid m aking it loo w ide.
The vertical colum ns are called g r o u p s or fa m ilie s. T h e re arc e ig h t
m ain (so called A ) g ro u p s and 10 subgroups (so called В groups). T h e e le ­
m en ts in A g ro u p s are called the r e p r e se n ta tiv e e le m e n ts and th o se in В
g ro u p s arc called the tra n sitio n elem en ts. T h e tw o series o f elem en ts below
the perio d ic table are called the in n er tran sition elem en ts.
T h e p ro p e rtie s o f H are n o t S in ce the elem en ts in a g ro u p have sim ila r chem ical p ro p erties, a few
e x a c tly th e sa m e as th o se com m on groups arc given fam ily nam es.
o f a lk a lie s, th e re fo re it is IA grou p elem en ts : L i, N a, K, R b, C s, F r => a lk a li m e ta ls
n o t in clu d e d in a lk a li m e t­
IIA g rou p elem en ts : Be, M g, Ca, Sr, B a, R a => a lk a lin e ea rth m e ta ls
a ls .
V IIA g rou p elem en ts : F, C l, Br, I, A t => H a lo g e n s
O r V ll l A g ro u p elem en ts : He, Nc, A r, K r, X e, R n => N o b el g a ses

I | R espresentative elem ents

| | Transition elem ents

liffl Lanthanide and A ctinide elem ents

И
—

'

FIGURE 6.19 C l a s s i ­
fication o f e le m e n t s in
p erio d ic table.
' i
■■■ii щШ ЩIf
Ш ■Iff!
220 Chapter 6

6.6.1 E L E C T R O N I C S T R U C T U R E AND P E R IO D I C TA BLE

T he sim ilarities betw een the chem ical properties o f elem ents in a group
arise from the sim ilar electron configurations in the outerm ost shell o f these
elem ents. Table 6.2 show s the electron configurations o f inert gases (Group
VIII A or O), alkali m etals (Group IA), and halogens (Group VIIA).

TABLE 6.2 The Electron C onfigurations o f Som e G roups o f E lem ents

IN E R T G A SE S or A L K A U M ETA LS or H A LO G EN S or
G R O U P VIDA G R O U P IA GROUP VB A
2H e : I s 2 3 Li : [He] 2 s 1 9F : [H e] 2 s 2 2 p S
10N e : [H e]* 2 s 2 2 p 6 n N a : [Nc] 3 s 1 17C1 : [N e] 3 s 2 3 p S
18A r : [N e]** 3 s 23 p 6 19K : [Ar] 4 s 1 3 5 B r : [A r] 4 s 23 d 104 p 5
3 6 K r : [Ar] 4 s 23 d 104 p 6 3 7 R b : [Kr] 5 s 1 53I : [K r] 5.s24 d 105 p S
5 4 X e : [Kr] 5 s 24 d , 0 5 p 6 55C s : [Xe] 6 s 1 85 A t : [X e] 6 s 2 4 f 145 d 106 p 5
g6 Rn : [Kr] 6 s 24 f 145 d 106 p 6 8 7 Fr : [Rn] 7 s 1
J
*[H e] is called the h e liu m core and re p re se n ts I s .
9 9 6
**[N e] is called the n e o n c o re a n d re p re se n ts I s 2s 2 p .

T h e in sp e c tio n o f T a b le 6.2 rev eals th at elem e n ts in a g ro u p h av e the

sam e nu m b er o f electrons in their outerm ost shells. Inert gases have eight e lec ­
trons (n s2n p 6 e x c ep t H e), alkali m etals have one electro n (n s1) and halogens
hav e sev en (n s 2n p 5) electro n s. W e see th a t the c h e m ic a l p ro p e rtie s o f ele ­
m en ts a re p rim a rily d e te rm in e d by the electro n s in the o u term o st sh e ll o f the
elem en t. T h ese e lectro n s a re c a lle d v a le n c e e le c tr o n s a n d the o u te rm o st
sh e ll o f the a to m is ca lled the va lence shell. T h e lo ss, gain o r sh arin g o f v a ­
lence electrons determ ines the chem ical properties o f an atom.

6.6.2 FIND IN G PER IO D AND G R O U P N U M B E R

Each period in the Periodic Table begins with s orbital and ends with p
orbital.
r
P eriod N um ber O rb itals B ein g F ille d N u m b e r o f E lem en t
Щ 1 s t p e rio d
F *1 Is 2
S' , 2p
4 3s 3p 2 n d p e rio d 2s2 p 8
M4s 3d - 4p |
Wis 4d 5p 3 rd p e rio d 3s3p 8
Щй: 5d 6p
4 1^ p e rio d 4 s3 d 4 p 18
17s 6d
5 1*1 p e rio d 5 s4 d 5 p 18
■v
6 1^ p e rio d " ^ 6 s4 f5 d 6 p 32
7 l11 p e rio d 7 s5 f6 d 7 p 32 J
A s w e can see the period n um ber o f an element is the principle quan­
tum number o f the outermost energy level (or valence shell). The total number
o f electrons in the valence shell determines the group n u m b e r . If the last
 Atomic Structure and Chemical Periodicity 221

electron o f the atom is in s o r p orbitals it is in the A group, if it is in d orbitals

it is in th e В group. T he follow ing exam ples illustrate tine su bject.
"I T h e o u term o st e n e rg y lev el o r v a ­
len c e sh ell o f N a is the 3rcl e n e r­
11 N a : l s ^ s Y p Y i s 1 3rd period IA group g y le v e l. T h e re is j u s t o n e e ' in
th e v a le n c e sh e ll so it is in the
1 s t g ro u p . S in c e th e la s t o rb ita l
is s it is a m e m b e r o f A group.

16'
,S : l s 22s 22 p 63s 23p 4 => 3rd period V IA group

3 d o rb ita ls do n o t
b e lo n g to th e v a ­
le n c e sh ell, th e re ­
31
G a : l s 22s 22p 63s 23p 64 s 23 d 104 p 1 4th period IIIA group fo re the ten e le c ­
tro n s in 3 d a re
n o t c o u n te d v a ­
le n c e e le c tro n s.

22T i : 1s 22s 22p 63s 23p 64 s 23d“ 4 th period IVB group

T h e last electron o f the titanium is in d orbital, therefore it is a m em ber o f

В group elem ents. In determ ining the group n u m b e r o f tran sitio n elem ents we
should co n sid er the s and d orbitals.
s2d* => IIIB s2d5 => VIIB s V 0 => IB
s2d2 => IVB s2d6 s2d10 => IIB
s2d3 => VB s2d7]=>VIIIB
s’d5 => VIB s2d8

F o r ex am p le : 29CU : 1s 22s 22 p 63s 23p 64 s 13 d 10 =» 4 lh period IB

EXAMPLE 6 . 2 4 F i n d i n g t h e L o c a t i o n o f E l e m e n t s in P e r i o d i c T a b l e
Problem : Indicate the period number and group number of each of the following atoms.
a) 14X b) 19Y c) 25L d) 35M
Solution :
a) 1 4 X : l s 22s 22p 63s 2 3p 2 => 3rd period IVA group
b) 19Y : IAr] 4 s 1 => 4 th period IA group (Recall | Ar] = l s 22s 22p 63s 23p6)
c) 23 L : [Ar] 4s 2 3d 3 => 4 dl period VB group
d) 45M : I Ar] 4s 23 d 104p 5 4 lh period VIIA group
- — -----------------------------------------------------------------------------------------------------------------

E X E R C I S E 6 . 3 3 Determine the period and group numbers of each of the following elements.
at i ()X b) 17 Y Ci 26 Z u ) 2 n(' l \ \ I I I A . I»3r,‘ l \ УПЛ, c)4thl \ V IIlll

EXAMPLE 6 . 2 5 C a l c u l a t i o n s B ased on P e rio d ic table

Problem : Determine the atomic number o f the element that is in the 4 ,h period and in VIA group.
Solution : Since the clem ent is in period 4 and in Group VIA, it has 6 electrons in the 4 energy level.
(4s 2.Art4). So we will write the electron configuration of the atom until it ends with 4p4.
X = 1ls72s 22p 63s 23pd4s 23 d 104 p 4 => 3 4 electrons = 34 protons o r Z = 3 4
Y S X i t ? ......
♦ ......
E X E R C I S E 6 . 3 4 What is the atomic number ot the 1 ment in period 3 and group IIIA ? 13
222 Chapter 6

EXAMPLE 6 . 2 6 C a l c u l a t i o n s R e l a t e d to t h e P e r i o d i c T a b l e
Problem : W hat is the place o f 13X' + in the periodic -table ?
Solution: In modern periodic table, the elements are arranged in order of their increasing atomic number.
W hen an elem ent loses or gains electron to form an ion, the num ber of protons (atomic number) does not
change. That is why the■pla ее of X and X3+in lib i table is the same. The period and groui ) numbers с all be found
by using the ato mi с runlibei•: 13X : l s 22s22p!’3s : la 1, it is toe a led in 3rti ]reriod and IIIA group.

E X E R C IS E 6 . 3 5 Л ! a ittf llT s liS y e ihe sai ne number ol eleelmiis. If the element A is in the 3n1 period-
11A group, whai: is ihe peril >d anti group numl ter ol В ? 2 "‘ VIA

E X E R C IS E 6 .3 6 t ПС ion Q " has IX el eel ro is. Find the location t?f Q in the per indie mine. pvt I\V .\

EXAM PLE 6 .2 7 С; i l e u l a l i o n s A s s o c i al e d w i t h P e r i o d i c T a b l e
Problemto.1 mol (>f rj X 3 weighs 120 u. If thi; numbers of protons and neutrons in
Ci the n uck 5US of the X
atom are equal, what is the group and period num beras of the alt>m X Cr= 52
! ?
Solution: ata •> MW' of CV2X3 -0 AW of X •-> number ol’ protons —> number of \
D periods and gf oup)S.
MW = m/n = 21) g/ 0.1 mol = 200 g/mol => Cr 2X 3 = 200 i=> 2x52 + 3X = 200 => >I = 32 g/miOl
A = p + n .jj j f T■;3 2.= p - t-p => p = 16 => I. \ : 1s-’?N: 2pf'3s 23p 4 => 3Td period, VIA group.

E X E R C I S E 6 . 3 7 Л 1- g of X :!H , ig ) (.)(ecu P's M i a ri u m e of 15 L a i 0.82 aim and 127-C. If X 1UlS; ccjuul

number o f proit >ns and neu irons, whal is its | liar e 111 (tie peril >dic table. ? 1-1=1 2mt j,
ЛУ '"Л jIft o up

6.7 PERIODIC PROPERTIES

E le m e n ts w ith in a g ro u p have id e n tic a l n u m b e rs o f v alen ce ele ctro n s,
th u s th ey h a v e sim ilar ch em ical b eh av io r. B u t across a p e rio d th e n u m b e r o f
valen ce electrons increase one by one from left to right, therefore w e m ig h t e x ­
p e c t a g ra d u a l c h an g e in c h em ic a l b e h a v io r. H o w e v e r, th e re is a re g u la r
ch a n g e in p ro p e rtie s o f ele m en ts w ith in a g ro u p o r w ith in a p erio d . T h ese
p ro p erties are : 1) A tom ic volum e or size 2) Ionization Energies 3) Electro­
negativity 4) Oxidation numbers SfM etalllc and nonmetallic properties.

6% 1 A T O M IC R A D IU S \
A n u m b e r o f physical and ch em ical p ro p erties o f elem en ts are related to'
the sizes o f atom s. Since all orbitals extend o u t to infinity, it is d ifficu lt to d e ­
term in e th e ato m ic radius o f elem ent. T h erefo re we, c an n o t g iv e e x a ct values
V o lu m e a n u m b e r o f shells
fo r a to m ic v o lu m es b u t ap p ro x im ate values. T h e a to m ic size is affected by
V olum e a 1 /n u c le a r ch arg e
m ain ly tw o factors 1) The number o f shells 2) N uclear charge.
S ince th e o rb ita l size in creases w ith in c rea sin g shell n u m b er, th en the
volume o f atoms is directly proportional to the num ber o f shells. As the nucle­
ar charge increases, the pull on the electrons increases and shells get c lo ser to
the nucleus, and consequently atomic volume decreases.
T h e v a r i a t i o n o f a t o m i c v o l u m e w i t h i n a p e r i o d : A ll the e le ­
m en ts w ith in a period h av e the sam e n u m b e r o f sh ells b u t the n u c le a r charge
in creases o n e b y one from le ft to right. T h e ato m ic v o lu m e is in v ersely p ro ­
p o rtio n a l to n u c le a r ch arg e, therefo re atom ic volum e decreases fr o m left to
 Atomic Structure and Chemical Periodicity 223

rig h t w ith in a period. If we co n sid er second period elem ents, all the elem ents
have tw o shells b u t n u c le a r ch arg e increases from +3 to + 10. So the lithium
has the largest volum e and N e has the sm allest volum e. F igure 6.20 illustrates
the relative sizes o f atom s in period 2 .

FIGURE 6.20 Atomic radii of the 2nd period elements. The decrease in size
can be attributed to the increasing nuclear charge across the period, and to the con­
stant number of shells each atom has.

The variation o f atom ic volum e within a group : P r o c e e d i n g

do w n a gro u p, atom ic v o lu m e ten d s to in crease b e cau se the n u m b e r o f shells
o f ato m s in creases one by one in each period. T h e in creasin g n u c le a r ch arg e
m ig h t lead u s to e x p e c t th a t electro n s w o u ld b e attracted m ore stro n g ly and
p u lled c lo se r to the n ucleus. H o w ev er, the in c re ase in th e n u m b e r o f sh ells
do w n a g ro u p also increases the repulsions betw een electrons in th e shells. A s
FIGURE 6.21 A t o m i c a resu lt the atom ic volum e increases dow n a group. T he ch ange in atom ic v o l­
radii o f g ro u p IA e le m e n ts.
um es o f IA g ro u p elem ents is illu strated in F ig u re 6 .21.T h e c h an g e in atom ic
volum e in p eriodic table is sum m arized in Figure 6.22.
volu m e d ecreases The ra d iu s o f a p o sitiv e ion is alw a ys less than the ra d iu s o f its p a r e n t
: > atom . W hen an electron is rem oved from a neutral atom , the average attraction
o f the nucleu s p e r rem aining electron increases, as a result a p o sitively charged
io n (catio n ) p o ssesses sm a lle r v o lu m e th an its p a re n t atom . S im ilarly w h en
_r electrons are added to a neutral atom , producing a negatively charged ion, both
FIGURE 6.22 Periodic 4 he a v erag e attractio n o f the n u c le u s p e r ele c tro n and the re p u lsio n s am o n g
trends in atomic volumes electro n s increase. B oth effects cause the radius o f a n egative io n to be g reater
of the elements. than th at o f the p arent atom . See F igure 6.23.
In iso e le c tro n ic io n s (io n s h av in g
N O N M E T ALS the sam e n u m b e r o f ele ctro n s), the
g r e a te r th e n u c le a r c h a rg e , th e
sm a lle r the ionic radius. F o r e x am ­
— Q ---- X ) - Q ple, 7N 3', 8 0 " ', 9F", ioN e, n N a +,
0.152 Lb' F 0.064 ^ B ^ F 0.136
i 2M g 2+. 1зА 13+ a re iso e le c tro n ic .
T h e N 3' has the g reate st io n ic ra d i­
^ ^ ^ ^ ^ 0 .1 8 6 N a" 0.095
us, A l3+ has the sm a lle st io n ic ra d i­
Cl 0.099 0.181
us.

0 Q
^ ^ Щ ^ ^ ^ О .2 3 1 К" в, 0.114 0.195

Л * - ,
^ ^ 0 .1 4 3 A|3+ 0 0 5

FIGURE 6.23 Volumes of cationr ns

224 Chapter 6

E X A M P L E 6.28 C o m p a r in g A to m ic a n d Io n ic V o lu m e s
Problem : Compare the volumes of each of the following pairs,
a) i iNa and n Cl b) 9F and 17C1 c) Na+ and F d) S2~, СГ c) K+, Ca2+
Solution :
a) n N a : l s 22s 22p 63s] —» Period 3, Group IA ; 17СЗ : ls 22s 22p 63s 23p 5 —> Period 3, Group VIIA
Both elements are in the same period. As we move from left to right across a period, atomic volume decreases.
Therefore, Na has larger volume than Cl.
b) 9F : ls 22s 22p 5 Period 2, Group VIIA ; 17C I : ls 22s 22pf> 3s23p 5 -» Period 3, Group VIIA
These elements are in the same group. As we proceed from top to bottom in a group, atomic volume increases.
Therefore, Cl has larger volume than F.
c) Na+, and F‘ arc isoelectronic. In isoelectronic pairs more negative (or less positive) ion has greater volume. So
F' has larger volume than N a+.
о
d) S " and СГ arc also isoelectronic. S has larger volume than СГ.
e) K+ and C a2+ arc isoelectronic too. Therefore K+ has larger volume than Ca2+.

EXERCISE 6.38 Select the species which has larger volume 111 each of the following.
a) Cl, Cl b) C l '. K* c) Na, Mg, Si dj Be, Mg, Ca e) P 3 , S2', Cl , Ar, К
:

6.7.2 IO N IZ A T IO N ENERGY
S ince n u cleus attracts electro n s, th en en erg y is required to rem ove the
electrons from an atom.
T h e a m o u n t o f e n e r g y r e q u ir e d to r e m o v e th e m o s t lo o s e ly b o u n d e le c ­
first io n iz a tio n en erg y (sh o w n by
t r o n f r o m a g a s e o u s a t o m is c a l l e d i t s
I]). T h is change m ay be represented fo r the elem ent X as follow s:
X (g) + energy (10 -> X + (g) + e ‘
T h e e n e rg y req u ired to rem o v e the second lo o se ly b o u n d e le c tro n is
called the seco n d io n izatio n en erg y (I2) and, to rem o v e the th ird , the th ird
io n iz a tio n en e r g y (I3) and so forth.
X + (g) + I2 -> X 2+ (g) + e-
X2+ (g) + I 3 -> X3+ + e-
T h e v ariatio n o f io n izatio n energies o f the tran sitio n elem en ts (d block
elem en ts) and the in n e r tran sitio n elem en ts is v ery irregular. T h e re fo re , the
d isscu sio n o f th e ir io n izatio n energ ies is beyond o u r schedule. H ere w e w ill
o n ly d iscu ss the io n izatio n energ ies o f the rep resen tativ e elem en ts (s and p-
block elem ents).
T ra n s itio n e le m e n ts do
n o t fo llo w p e rio d ic tre n ­ T h e v a r ia tio n o f first io n iz a tio n e n e r g ie s w ith in a p e rio d : T he
ds in th e first io n iz a tio n ionizatio n energ y is the energy required to rem ove an electron from the attrac­
e n e rg ie s . tio n o f the n u cleus. A s the atom ic volum e increases the attractio n o f n u cleus
on the electrons decreases. (F ak.qjqT /r2). T herefore atom ic volum e and io n iza­
tion en erg y o f an atom is inversely p ro p o rtio n al to one another. A s a result o f
this ex p lan atio n w e deduce t h e i o n i z a t i o n e n e r g y i n c r e a s e s f r o m l e f t t o r i g h t
w i t h i n a p e r i o d b ecau se the atom ic v o lu m e decreases in the sam e direction.
I.E n e rg y a 1 /v o lu m e
T h e irregularites w ithin a period to this general rule are prim arily related to the
stab ility o f electro n s in half-filled and com p letely filled orbitals. A n clem en t
h a v in g a c o n fig u ra tio n e n d in g w ith s 2 (IIA gro u p ), s 2p 3 (V A g ro u p ), and
 Atomic Structure and Chemical Periodicity 225

s 2p 6 (V IIIA group) possesses h ig h e r io n izatio n en erg y th an the io n iza tio n e n ­

ergy o f the elem ent that follow s it in the periodic table. So the increasing order
o f ionization energies o f elem ents in a period is as follow s.
IA < IIA < IIIA < IV A < V A < V IA < V IIA < V IIIA (expected)
IA < IIIA < IIA < IV A < V IA < V A < V IIA < V IIIA (A ctual)
See F ig u re 6.24 for th e n u m erica l valu es in k ca l/m o l fo r the io n izatio n
energies o f the second and third period elem ents.

IA IIA IIIA IVA VA VIA VIIA VIIIA

ns1 ns 2 ns 2np 1
2 2 ns 2np 3
ns np ns 2np 44 ns 2_/5
np ns 2np 6
3 4 5 6 7 8 9 10
Li Be В с N О F Ne
124 214 191 260 335 314 402 497

11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
118 175 138 188 254 239 300 363
4
FIGURE 6.24 The First Ionization Energies for the second and third period
elements.

V a r ia tio n o f io n iz a tio n e n e r g ie s in a g r o u p : T h e e le m e n ts in a
I. en erg y in creases group have the sam e co nfiguration ending, and th e ir atom ic v o lum es increase
оa -n ------------->
43 Г dow n the group. A y a result o f increase in volume down a group the ionization
energies o f the elem ents decreases. F o r G ro u p I A the io n iz a tio n energ ies o f
the elem ents are :

P eriod N um ber 2 3 4 5 6 7
FIGURE 6.26 V a r ia ­
tion of the first ionization E le m en t Li Na К Rb Cs ' Fr
energies in the periodic I] (k cal/m o l) 124 118 9 9 .3 9 7 .0 9 0 .0
table. J

F ig u re 6.25 show s the v a ria tio n o f io n iz a tio n en e rg ie s o f atom s w ith

atom ic n u m ber. F igure 6.26 show s the g eneral trend in io n izatio n energ ies in
the periodic table.

FIGURE 6.25 A grap­

hic illustration of varia­
tion of the first ionization
energy with atomic num­
ber. Note that nobel gas­
es have high ionization
energies, whereas the
alkali metals all have low
ionization energies.
226 Chapter 6

S u c c e s s iv e I o n iz a tio n E n e r g ie s : So fa r w e h av e d isc u sse d o n ly the

first io n iz a tio n energies. A fter one electro n is rem oved from a n eu tral atom ,
th e v o lu m e o f th e m onopositive ion b ecom es sm aller, and the attraction o f n u ­
cleu s p e r e le c tro n increases. T h erefo re m ore en ergy is n eed ed to rem o v e an
e le c tro n from a p o sitiv ely charged ion. So the io n iza tio n en erg ies alw ays in ­
cre a se in th e fo llo w in g o rd e r : I i < I 2< l 3 ... I n. i < I n
F o r m agnesium atom the first three ionization energies are:

Mg(g) ( ls 22s 22p 63s2) + 176 kcal -> Mg+(g) ( ls 22s 22p 63s1) + e- (Ii=176 kcal/mol)
M g+(g) ( ls 22s 22p 63sx) + 347 kcal —> Mg2+ (g) ( ls 22s 22p6) + e" (I2=347 kcal/mol)
Mg 2+(g) ( ls 22s 22p6) +1848 kcal -> Mg 3+(g) ( l s ^ s ^ p 5) + e ' (I3 =1848 kcal/mol)

A s w e see Ij < I 2 < I3. T h e first and second io n iz atio n energ ies fo r m ag ­
n esium atom b elong to the rem oval o f the electrons in the v alence shell o f the
atom (3s2). H ow ever, the third electron requires considerably m ore energy for
rem oval relative to the valence electrons. T his sharp in crease in ionization en ­
erg y reflects that the third e lec tro n is n o t an o u te r sh ell ele c tro n (o r v alen ce
electro n ) b u t an in n e r shell electron. T h is e lectro n is in a c lo se r o rb ita l to the
n u cleu s (2p) than 3s. T h e re fo re m ore en erg y is req u ired . If w e th in k o f N a
( l s ^ s ^ p ^ s 1) w e w ould e x p ec t I2 :> Ij, b ecau se th e first electro n w ould be
rem o v ed from 3s (outlier shell o r v alence shell), b u t the second electron from
2 p (an in n e r shell). F o r alum inum ( l s 22 s 22 p 63s 23 p 1), I 4 :> I 3. T o rem ove the
fo u rth e le c tro n from a lu m in u m atom , a level c lo se r to the n u c le u s m u st be
broken. H ere w e have considered ju s t three elem ents, N a, M g, and A l, b u t the
sam e kind o f in fo rm atio n can be ob tain ed from th e electro n con fig u ratio n s o f
the other elem ents.
T A B L E 6.3 T he S u ccessive Io n iza tio n E nerg ies o f the F irst 20 E lem en ts.
(The trammed values indicate the sharp increase between ionzation energies)

Atomic Ionization Energy (kcal/mol)

Number Atom 11 *2 U 15 16 Is
1 11 3 1 3 .5
2 He 5 6 6 .9 1254
3 Li 124.3 1744 28 23
4 Be 2 1 4 .9 4 1 9 .9 35 48 50 20
5 В 191.3 5 8 0 .0 874.5 5 98 0 7842
6 С 2 5 9 .6 5 6 2 .2 1 104 1487 9039 1 1294
7 N 335.1 68 2 .8 1094 1786 2257 12726 15375
8 О 314.0 8 1 0 .6 1267 1785 2 62 6 3184 17013 2 08 7
9 F 4 0 1 .8 80 6 .7 1445 2012 2633 3623 4268 219.89:
10 No 4 97 .2 9 4 7 .2 1500 2241 2915 3641 - -

11 Na 118.5 1091 1652 2280 31 96 3975 4806 60 92

12 Mg 176.3 3 4 6 .6 1848 2521 3256 4310 5 19 5 6134
13 Al 13 8.0 434.1 655.9 2767 3547 4390 55 78 6574
14 Si 187.9 37 6 .8 771.7 1041 3844 4729 6097 7008
15 P 25 4 4 5 3 .2 695.5 1184 1499 5082: 6071 7132
16 S 2 3 8 .9 54 0 807 1091 1672 20 29 6480 75 82
17 Cl 300.0 5 4 8 .9 920.2 1230 1563 2230 2636 .8031
18 Ar 363.4 6 3 7 .0 943.3 1379 1729 21 05 2859 33 09
19 К 1 00 .1 7 3 3 :6 1100 1405 1905 2 29 9 2721 3 57 4
20 Ca 140.9 27 3.8 1181 1550 1946 2513 2952 33 9 0
 Atomic Structure and Chemical Periodicity 227

EX A M P LE 6.29 C o m p a ris o n o f Ionization Energies

Problem : Which atom in each of the following pairs of atoms would have the lower first ionization energy ?
a) Na, К b) Na, Mg с) P, Cl d) Ar, К с) N, О
Solution : The easiest way to compare the ionization energies of elements is to locate these elements in a
miniature periodic table, and use periodic variations of ionizations energies in the periodic table. Recall that ioni­
zation energy increases stepwise from left to right across a period with the exceptions of IIA (s2) and VA (s 2p5)
groups. It decreases from top to bottom in a group.

IA ПА HI A IV A VA VIA V IIA V IIIA

a ) Ijs'a > I k
l slP
b) I.Vtg > Ua
2 nd P N О C ) Ia > Ip
3 fdp Na Mg P Cl Ar d) U r > U (Ar Is an Inert gas)
К e) I \ > lo (N has s2p 3 configuration)

E X E R C ISE 6 . 3 9 Arrange the following atoms in order of increasing their first ionization energies. 9F,
K)Ne, iiN a . / д а <!/•’<h \e

E X A M P L E 6.30 C o m p a rin g Atomic Volumes a n d Ionization Energies

Problem : Given the elements 9X, ] 5Y, ] 6Z, 19K, 2o U 37M. a) Arrange them in order of increasing atomic
volumes, b) List them in order of increasing their first ionization energies, c) How many valence electrons does
each elem ent have ? d) Which one of these atoms has the highest second ionization energy ? The highest third
ionization energy ?
Solution : We will first locate these elements in a miniature periodic table.
9X : ls 22s 22 p 5 2nd period, VIIA Group IA ПА 11IA IV A VA V IA VIIA VHIA
)5Y : ls 22s 22p 63s 23p 3 => 3rd period, VA Group l stP
16Z : hoNc] 3s23p 4 => 3rd period, VIA Group 2 rd P
lillllll:
X
19K : [Ne] 3s 3p 4s => 4in th .period IA Group
3 rd P Y Z
20L : tisAr] 4s 2 => 4 th period IIA Group
4 lh P К L
37M : [isAr] 4s 23d 104p 65 s 1 => 5th period IA Group ;
5 th P M

a) Comparing the volumes of elements we may say that VM>VK and V /> V y and combining these we may write
the following order: V x < V ^ < V y <V l <V k <V m
b) The ionization energy is inversely proportional to the atomic volume. But the existence of completely filled
(s2, s 2p6...) or completely half-filled (p3, d5...) orbitals increases the ionization energy of the atom. Thus
2 3
Y has s p c o n fig u ra tio n en d in g th ere fo re its io n iz a tio n
Ix > I y >I z > I i > I k > I.M
energy is greater than the elem en t ju s t follow ing it, Z.
c) The electrons in the outermost energy level or shell are called valence electrons. Therefore the number of va­
lence electrons are
X —> 7 valence c" Z —>6 valence e ' L —> 2 valence e ‘
Y —> 5 valence e' К -» 1 valence e" M —> 1 valence e'
d) (1) The valence electrons are the most loosely held electrons by the nucleus of the atom. Therefore they may
be removed easily relative to the electrons in the inner shells. The elements having just one valence electron (IA
group) have the highest second ionization energies. The first ionization energy of the К is greater than that, of
M. Therefore К also has the highest second ionization energy among these elements. (2) The elements having
two valence electrons (IIA group) have the highest third ionization energies. So L has the highest third ionization
energy.
228 Chapter 6

EXER C ISE 6.40 Compare the atomic volumes and ionization energies of the elem ents 9X, 17Y, 13Z,
11R. 37L.

E X A M P L E 6.31 U n d e r s ta n d in g Io n iz a tio n E n e r g ie s o f A to m s
Problem : The successive ionization energies in kcal/mol of X, Y, Z and Q elements are given below.
Element h 12 l3 a) Find the number of valence electrons of each elem ent
14 1
X 2 15 420 3548 5020 b) W hat is the group number o f Q?
Y 118 1091 1652 2280 c) W hich elem ents would you expect to have sim ilar
Z 141 274 1181 1550 chemical properties?
I Q 300 548 920 1230y

Solution : a) W hen the successive ionization energies of X are compared, we observe a sharp increase be­
tween I2 and I3. This reveals that X has two easily removed electrons or two valence electrons. Similarly we may
deduce that Y and Z have one and two valence electrons respectively. But we cannot say anything about the num­
ber of valence electrons o f Q because any sharp increase between two successive ionization energies is not seen
among the first four ionization energies. W hat we can say about it is that it has at least four or more valence
electrons.
b) The number of valence electrons of A group elements is equal to the group number of the element. The num­
ber o f valence electrons of Q is unknown. Therefore its group number is also unknown (at least four)
c) The elem ents with the same number o f valence electrons (the same group elements) have sim ilar chemical
properties. Hence X and Z have similar chemical properties.

E X E R C IS E 6.41 The four successive ionization energies'in kcal/mol of an clem ent is 191, 580, 875,
and 5980. How many valence electrons docs this clement have ? In which group of the periodic table is this cle-
mcnt located ?_________________________________________________ ’ 3 ,IIIA

6.7.3 O T H E R P E R IO D IC P R O P E R T IE S
A - E le c tr o n eg a tiv ity : T he ten d en cy o f an a to m to a ttra c t electro n s is
c a lle d its e le c tro n e g a tiv ity. T h e e le c tro n e g ativ itie s o f the ele m e n ts are in ­
fluenced b y th e sam e factors w hich affect the ionization energies. T he g rea ter
the ionization energy o f an atom the greater the electronegativity o f the atom.
B - O x id a tio n N u m b er s : W e have seen th a t th e in ert g ase s h av e e x ­
I f a. c o m p o u n d is fo rm ed
tre m e ly h ig h io n iz atio n en erg ies. T h is in d icates th at th e se ele m en ts are v ery
by e le c tro n tra n s fe r fro m
o n e a to m to th e o th er, it stable. In fact the rest o f the elem ents com bine w ith each o th e r to reach one o f
is c a lle d i o n i c com ­ the in e rt gas electro n p o p u latio n by gaining, lo osing o r sh arin g electrons. F o r
pound. The com pounds exam ple let us consider Ca and Cl elem ents.
b e tw e e n IA g ro u p e le ­ 2oCa : l s 22 s 22 p 63s 23p 64 s 2
m en ts and V IIA gro u p e le ­
17C 1 : 1 s 22 s 22 p 63 s 23 p s
m e n ts a re io n ic c o m ­
p o u n d s . I f th e e le m e n ts In ert gases all h ave the sam e co n fig u ratio n ending n s ^ p 6 (except H e, Is 2) So,
th a t c o m b in e b o th h a v e calciu m h as tw o m ore electro n s th an the n e a re st in e rt gas A r, and Cl has one
h ig h io n iz a tio n e n e rg ie s , less e lectro n th a n the n e a re st in e rt gas. C h lo rin e n e ed s o n e m o re e le c tro n to
th e y te n d to s h a re e le c ­ reach arg o n -lik e electro n p o p u latio n , and calciu m m u st give tw o electro n s to
tro n s to re a c h in e rt g a s
reach arg o n -lik e electro n population. W h en calcium and ch lorine are b ro u g h t
lik e e le c tro n p o p u la tio n .
to g eth er this electron loss and gain takes place procuding C a2+ an Cl" ions, and
T h e c o m p o u n d s b e tw e e n
s u c h e le m e n ts a re c a lle d th ese io n s a ttract e ac h o th e r to form C a C l2. T h e ch arg es o n th e C a 2+ and СГ
c o v a le n t com pounds are c a lle d o x id a tio n n u m b e r s . T h e o x id a tio n n u m b e rs o f e le m e n ts are
o r m o le c u la r co m p o u n d s.
 Atomic Structure and Chemical Periodicity 229

closely related to their electronic structures. T h e possible oxidation num bers o f

elem ents are listed in T able 6.4.
T A B LE 6.4 O xid a tio n N u m b e rs o f A G roup E le m e n ts
f
G ro u p n u m b er IA IIA П1А IVA VA VIA VIIA V1IIA ^
O u te r shell
s 1 s2 s V s2 p 2 s2 p 3 s 2P 4 s2 p5 s2 p 6
c o n fig u ra tio n
O xid atio n 1 + 2 + 3 + 4+ 3- 2 - 1-
n u m b er ( 2 +) (3+) (4+ ) (5 + ) 0

(4-) (5+ ) (6 +) (7 + )
V v J

A t the very beginning o f this course w e learned the oxidation num bers o f
very co m m on cations and anions. R ecall that these oxidation num bers m ay be
used to d eterm ine the form ulas o f the com pounds.
C- M eta llic an d n o n m e ta llic p ro p erties : T h e m eta llic p ro p ertie s o f
an elem en t depends on the ease w ith w hich elem ents release electrons. So the
elem ents w ith low ionization energies reflect the m etallic properties w ell. T he
elem en ts in th e IA, IIA and IIIA groups have q u ite low io n iz atio n en erg ies,
th erefo re they are m etals. M etals only give electrons to reach inert gas like
electron number and produce positively charged ions in reactions. On the other
h and the elem ents in the IV A , V A , V IA , V IIA g ro u p s m ay g a in o r lo se e le c ­
trons to reach inert gas-like electron population. T h e elem ents in these groups
are n on m etals. T he inert gases are also nonm etals. So the m etallic pro perties
d ecreases from left to right across a period, and increases from top to bottom
w ithin a group. T he oxides o f m etals produces bases w hen reacted w ith water.
T he oxid es o f n o n m etallic elem en ts pro d u ce acids w hen reacted w ith w ater.
Therefore m etal oxides are called basic oxides and nonm etallic oxides are
called acid oxides. Hence the acid character o f the oxides o f elem ents increases
from le ft to right across a period. M o st o f the perio d ic p ro p erties o f elem ents
are su m m arized in Figure 6.27.

Atomic volumes decrease

Ionization energies increase
Electronegativities increase
>
Nonmetallic properties increase
---------------------------------------- 4 n onm etals

о Transition elements
P*
сi-
G.
О

E
О <
<

FIGURE 6.27 Periodic properties

230 Chapter- 6

EXA M PLE 6 . 3 2 U n d e rs ta n di n g Periodic Properti es

Problem :
—
— — . ...
-

....

X
y F z L
Q
M

a) Which element has the greatest volume ? Which one has the smallest volume ? b) Which element has the
most metallic character, which one has the most nonmetallic properties ? c) Which one has the greatest first ioni­
zation energy, which one has the smallest first ionization energy ? d) W hat are the oxidation numbers of each of
these elements '? c) What are the formulas of the compounds formed betwecd X and L, Y and M elements ?
Solution :
a) Element X has the greatest volume, and Q has the smallest volume.
b) Element X is the m ost metallic one, and Q is the most nonmetallic one.
c) Element Q has the greatest first ionization energy, X has the smallest first ionization energy.
2 - o r 6+
d) X 1+ , Y2+ , Z4+ or4‘ Q k 7 + , m ‘-
e )X 1+ L2- X2L and Y2+ M 5 > YM 2

X
 Atomic Structure and Chemical Periodicity 231

SOME NEW TERMS

Ampere (A) is the SI unit for current; quantity Law of m ultiple proportions states that
of electric charge passing through a point per second. whenever two elem ents form more than one com ­
Anode is an electrode at which an oxidation reac­ pound, the different masses of one elem ent combines
tion occurs. with the same mass of the other are in the ratio of
small whole, numbers.
Atomic number is the num ber of protons in a
nucleus. Mass number is the numerical sum of the pro­
tons and neutrons in an atom of a given element.
Cathode is an electrode at which a reduction reac­
tion occurs. Mass spectrometer (mass spectrograph) is
a device used to measure precisely the quantities and
Cathode rays are negatively charged particles
masses of the different ions in a beam o f positively
(electrons) emitted at the negative electrode in the pas­
charged gaseous ions.
sage of electricity through gases at low pressure.
Neutron is an electrically neutral fundamental
Coulomb is the am ount of charge that passes a
particle found in the nucleus o f an atom, except H
fixed point along a wire when a current o f 1 amp
atom.
flows for 1 second.
Orbital is a particular electron waveform with a
Electrolysis is a chemical change caused by the
particular energy in an atom.
passage o f electricity through a molten ionic com ­
pound or through a solution that contains ions. Orbital diagram is a diagram show ing an
atom's orbitals in which the electrons are represented.
Electron is a subatom ic particle carrying the
fundamental unit of negative electrical charge and Period is a horizontal row of the periodic table.
found outside the nucleus of an atom. Periodic table is an arrangem ent of the elements
Exclusion Principle o f Pauli states that in which elements with similar physical and chemical
no two electrons may have four quantum numbers in properties are grouped together.
an atom. Photon is a"packagc" of energy in electromagnet­
Faraday is the quantity of electrical charge asso­ ic radiation.
ciated with 1 mol of electrons (96500 coul / mol 6) Proton is a fundamental particle carrying the bas­
Frequency is the number of cycles per second of ic unit of positive electric charge and found in the nu­
electromagnetic radiation. cleus of an atom.

Group is the vertical column of elements in the Shell (or energy level) refers to the collec­
periodic table. tion of all orbitals having the same value of n.

Hund's rule stales that w henever orbitals of Spectrum is the display produced by an instru­
equal energies arc available, electrons are assigned to ment designed to separate or disperse light into its
these orbitals before any pairing of electrons occurs. component colors.

Ionization energy is the energy needed to re­ Subshell (or sublevel) is a collection o f o r­
move an electron from an isolated gaseous atom, ion, bitals of the same type.
or molecule. Valence electrons are the electrons in the va­
W Isotopes are atoms of the same elements having lence shell of an atom.
different mass numbers caused by differences in their Valence shell is the shell with highest princi­
numbers of neutrons. pal quantum number, (n) in an atom.
Law of definite proportions states that the Wavelength is the distance between crests (or
elements are always combined in the same proportion troughs) in a wave.
by mass in a given compound.
232 Chapter 6

R E V IE W Q U E S T IO N S

6.1 W hat are the contributions o f each of the fol­ 6.13 W rite the quantum numbers of each electron
lowing to the atomic theory o f matter ? found in an nitrogen atom.
a) Dalton b) Rutherford c) Faraday
d) Thomson e) Chadwick f) Bohr 6.14 W hat is a group in the periodic table ? W hat
g) Heisenberg h) Planck is a period ? How many elements are there in each of
the first six periods ? Give an alternate name for each
6.2 W hat are the fundam ental particles o f an of the following groups o f elements : IA, IIA, VIIA,
atom? W hat are the relationships among them ? VIIIA.

6.3 W hat is an isotope? Com pare the following 6.15 W hich property o f an atom is m ore closely
properties of isotopes. related to its chemical behavior, atomic mass or atom­
a) Atomic number b) Atomic mass number ic number? Explain.
c) Proton number d) Neutron number
6.16 W hat is the valence shell in an atom? W hy
e) Physical properties f) Chemical properties
is it important?

6.4 Explain why atomic weights of elem ents of­

6.17 W hat are the eight types, of configuration
ten differ from whole numbers, even though atoms
found for the eight main groups of the periodic table?
contain whole numbers of protons and neutrons.

6.5 How doe's the Bohr model of the atom differ 6.18 W hy do elements in the same group display
rather similar chemical properties?
from Rutherford's model ?
6.19 Explain the general trend in atomic radii as
6.6 Describe briefly the essential differences be­ you go across a period in the Periodic Table.
tween Bohr and present-day models o f the atom.
6.20 Lithium has an atomic radius of 1.52 A° and
6.7 W hat are the names of the four quantum num­ ionic radius of 0.65 A°; fluorine has an atomic radius
bers of an electron? W hat arc the permitted values for of 0.71 A 0 and an ionic radius of 1.36A°. Explain
each of them? why Li decreases in size on becom ing an ion while
fluorine increases in size.
6.8 W hat is the significance of the division o f a
shell into orbitals? How many orbitals are there in 6.21 W hat are isoelectronic ions ? W hy should
each shell? the series S2', СГ, Ar, K 1+, Ca2+ show a steady de­
crease in size ?
6.9. How many electrons may be accommodated
in each shell? in each orbital? Why ? 6.22 W hich group of elem ents in the Periodic
Table would you expect to have low first and second
6.10 W hy do we always tabulate ground-state el­
ionization energies with very high third ionization en­
ectronic configurations, rather than excited states?
ergies ?
6.11 W hat is a continous spectrum ? How does it
differ from an atomic spectrum ? 6.23 Explain the fact the second ionization energy
of boron is greater than the second ionization energy of
6.12 W hat are the rules for w riting the electron beryllium, whereas the first ionization energy o f boron
configurations o f atoms ? is less than the first ionization energy of b<iryllium?
 Atomic Structure and Chemical Periodicity 233

R E V IE W P R O B L E M S
The Law of Definite Proportions
6 .2 4 In a co m p o u n d o f Cr and O , the ratio o f 6 .2 8
chrom ium to o x y g e n by m a ss is 1 3 /6 . H ow m any
grams o f Cr are needed to produce 57 g o f this chrom i­
um o x id e ? 39 g

6 .2 5 In a com pound o f X and Y , the d efin ite pro­

portion by m ass is 3 /2 . If 15 g o f X and 12 g o f Y are
reacted, w h ich elem en t and h ow m any gram s remain
unreacted? 2 g of Y

The g iv en graph indicates the relationship b etw een

6 .2 6 In c o m p o u n d X 4 Y 3 , m x /m y = 3 /1 . If the the m asses o f the com p ou n d X 2 Y 3 and Y in the co m ­
pound.
m olecular w e ig h t o f the com pound is 144 g /m o l, find
a) W hat is the co n sta n t proportion b etw een the
the atom ic w eig h t o f X and Y . 27, 12
m asses o f elem en ts X and Y in the com pound ?
6 .2 7 T he p ercen tage by m ass o f X in com p ou n d b) If the atom ic w e ig h t o f Y is 16 g /m o l, w hat is
X Y 2 is 2 0 %. W hat is the percen tage o f X in c o m ­ the atom ic w eig h t o f X ?
pound X 3 Y ? 60 % m x/m y =7/3,56 g/mol

The Law of M ultiple Proportions

6 .2 9 Sulfur form s tw o d ifferen t com p ou n d s w ith С w hich com b in es with the sam e am ount o f H is 4/3
oxygen . T h e percentage o f sulfur in th ese com pounds W hat is the form ula o f X ? C 3H S
are 5 0 % and 4 0 %, P rove that th ese data are c o n sis­ 6 .3 2
tent with the law o f m ultiple proportions.

6.30 M a n g a n ese and o x y g e n form tw o d ifferen t

com pounds. In the first com pound, 5.5 g o f M n c o m ­
bin e w ith 3 .2 g o f O . In the seco n d on e, there are 2 .2
g o f M n and 2 .2 4 g o f O. If the form ula o f the first
one is M n 0 2 , w hat is the form ula o f the second one? A graphic representation o f the rela tio n sh ip b e­
M я2 О7 tw een the m a sses o'f N and H in tw o d ifferen t c o m ­
pounds is g iv en . If II represents N H 3 , w hat form ula
6 .3 1 In the com p ou n d s C 2 H 4 and X , the ratio o f d oes I represent ? N2H4

The Law of C onstant V o lum es

6 .3 3 A m ixture o f 6 0 L o f hydrogen and 6 0 L o f 6 .3 4 H ow m any liters o f HCI (g ) m ay b e p ro­
air are reacted to g iv e H nO (1). W hat is the final v o l­ duced from 5 liters o f H 2 and 10 liters o f CI2 . A ssu m e
um e, if the temperature and pressure are held constant? no change in conditions o f pressure and temperature.
(1/5 o f air by v o lu m e is o x y g en ) 84 L 10 L
234 Chapter 6

Faraday's Laws of Electrolysis

6.35 How m any Faraday's and how many cou­ an unknown metal Y. After a while 6.9 g o f lead and
lombs o f electricity are required to deposit 1 mol of 0.6 g o f metal Y have been deposited. If the atomic
atom from weight of Y is 27 and Pb is 207, what is the charge
a) a solution containing Cu2+ ions on the ions of Y ? 3
b) a molten salt containing Cr3+ ions
6.41 A current of 5 amp deposits 1.517 g of P t in
6.36 A current o f 3.86 A is passed for 200 min 10 minutes from a solution of platinum salt. Find the
through an electrolytic cell containing molten F eC ^. equivalent mass o f the platinum ? 48. 8 g
Calculate the quantity of products formed at the elec­
trodes. 8 . 9 6 g Fe, 1 7 . 0 4 g CI 2 6.42 A 500 mL o f 0.5 M СиС1г solution is elec­
trolyzed by a current o f 9.65 A for one hour. The prod­
6.37 In the electrolysis o f molten A1F3, 1.12 L ucts are Cu and CI2.
of F 2 gas at 0°C and 2 atm are liberated. How many a) Calculate the quantity o f Cu deposited al the ca­
grams of Al will be deposited at the cathode ? thode.
(Al = 27) 1.8 g b) W hat is the volume o f CI2 at STP liberated at
the anode ?
6.38 The reaction occuring at one o f the elec­ c) W hat are the molar concentrations o f Cu2+ and
trodes during the charge of lead storage battery is : СГ ions at the end of electrolysis ? (Assume that the
P b S 0 4 (s) + 2e -> Pb (s) + SO2' (aq) volum e o f the solution does not change during the
How long would it take to produce 24.84 g o f Pb by a electrolysis.) a)ll.52g,4.032L,
current o f 0.50 A. Pb = 207 772 mi n c ) [ C u 2+] = 0 . 1 4 M , [ C l ' ] = 0 . 2 8 M

6.39 A constant current flows through two elec­ 6.43 Chromium plating is used to protect metals
trolytic cells connected in series. One contains molten from rusting. It is applied by electrolysis to objects ac­
F eC l 3 and the second molten MgCl2, and 14 g of Fe cording to the reactio n :
is deposited in the first cell. How many grams of Mg Cr 20 2' (aq) + 14H+ (aq)+12e‘ -> 2Cr (s)+7H20 (1)
are deposited in the second cell? Fe=56, Mg=24 9 g How long would it take to apply a chromium plating
of thickness 0.1 mm to an object of surface area 210
6.40 Two fused metal salts are electrolyzed in ser­ cm 2 in an electrolysis cell carrying a current o f 26 A?
ies. One is lead (II) iodide, the other is compound of The density o f chromium is 7.2 g/cm 3. 1 .8 h

. j— V
F u ndem antal Particles of Atom s and Isotopes
6.44 Indicate the num ber of protons, neutrons, age abundances of these isotopes are 90.9 % (Ne-20),
and electrons in each of the following. т-t»5' 0.3 % (Ne-21), and 8.88 % (Ne-22). Calculate the av­
a ) ^ N .' Ь )§ > А Ц с ) |||.£ d X ^ U ^ V T ) erage atomic mass o f Ne. 2 0 .2 g / m o l

6.47 The elem ent lithium consists o f two iso­

6.45 Natural chlorine compounds contain chlorine
topes. L i -6 and Li-7. W hat are the natural abundances
in the form o f the isotopes 35C1 (75.5% by mass)
of these two isotopes if the average atomic mass of
and 37C1 (24.5% by mass). C alculate the average
lithium is 6.9? 10% Li-6,90%Li-7
atomic mass of natural chlorine ? 35.49

6.48 An isotope with atomic mass 60 has 33 neu­

6.46 The elem ent neon consists o f three isotopes
trons in its nucleus. W hat are the name and chemical
whose atomic masses are 20, 21 and 22. If the percent-
symbol of the elem ent ? 27, c o b a l t ( Co)
 Atomic Structure and Chemical Periodicity 235

6.49 How many protons, neutrons and electrons 6.54 How many neutrons are there in N H l.+ ?
d o c s f ^ ^ r have? 2 4 - 28- 18 ( > , JH ) ' 7

6.50 Z2+, L3', X4+, Y3+ are isoelec.tronic. If the 6.55 XO?" has 50 electrons and 48 neutrons. What
16
atomic number o f X is 40, what are the atomic num ­ is the atomic mass number of X ? g О 31
bers of Y, L, Z elements? 39,33,38
6.56 If Y2' gives four electrons to X7+, both will
6.51 have 22 electrons. Determine the atomic numbers of X
Z A n . e- n u c le a r charge and Y. 24;25
P
X Aj 12 12

Y 16 32 6.57 0.1 mol of X 20 5 weighs 14.2 g. If X has 16

z 2+ 13 1 0 ' neutrons, what is the atomic number of X? 15

L3- 14 7+
6.58 X O 2 (s) + 4NaOH (aq) —>
which are isotopically related. N 34X 0 4 (aq) + 2H 20 (1)
3.6 g of X 0 2 and 800 mL of 0.3 M NaOH completely
6.52 Fill the blanks in the following table. react with each other. If X has 14 neutrons, what is its
atomic number ? 14
9 k
о

14 N 3- 31 p5+
15r m
a

P ? 9- ? ' "18 ?тд 6.59 The density o f X 2O 3 (g) is 1.9 g/L at 0.82
n ?^~ 2 16 2 2 24 45 atm and 127°C. If X 3‘ has the same number of elec­
e ? to ? 1Ъ ? « 18 ? • trons as ^M g ^* does, and contains equal number of
charge
of atom ? <2 r - ? <S? 0 \3 + 1- protons and neutrons, how many neutrons does X
A ?W ? 3? ? ЧС ? 9Г 80 have? 7
Z ? Ъ 7 /5 ? V% ■?«o
6.60 20.7 g o f K 2X O 3 is used to prepare a 600
mL of solution in which [K+J - 0.5 M] If X has equal
6.53 15r ^ aai^ X ^ h a v e the same number of elec­
,<P3+ num ber o f protons and neutrons what is its atomic
trons. W hat is the atomic number of X? 9 number ? K=39, 0 = 1 6 6

A tom , Light and Bohr's Model

6.61 Our eyes are sensitive to the light with the 6.64 M icrowaves are used to heat food in micro­
frequencies between 4 .0 x l0 14 and 7 .5 x l0 14 Hz. Calcu­ wave ovens. The microwave radiation is absorbed by
late the wavelengths in A° and energies in kcal/mol of the water in the food. This heats the water and there­
these two frequencies. fore the food becomes hot. How many photons with a
7 5 0 0 A ° , 4 0 0 0 A °;38.16 kcal 71.55 kcal wavelength of 2.5 mm would have to be absorbed by 1
6.62 Sodium vapor lamps are often used in resi- g water to raise its temperature by 100°C?
2 4
dental street lighting. They give off a yellow light 5.3x10
having a wavelength o f 589.4 nm. W hat is the fre­ 6.65 Calculate the following properties of a pho­
quency and energy of this light. ton em itted by a hydrogen atom when its electron
5 . 0 9 x 1 0 14 Hz, 48.6kcal/m ol drops from the n=5 to the n=2 state.
6.63 A photon emitted by mercury atom has the a) energy b) frequency c) wavelength
wavelength of 4.35xl(T 7 m. W hat is its frequency? In d) the region of the electromagnetic spectrum
which region does this radiation fall in the electromag­ a)65.9 kcal/m ol b ) 6 . 9 2 x l 0^ 4 H z
netic Spectrum ? 6 . 8 5 x l 0 14H z v i s i bl e c ) 4 . 3 4 x l O'7m
236 Chapter 6

6.66 Calculate the energy required to excite an the n =2 level cause the production of spectral lines in
electron from the n = 1 to the n = 4 level o f atomic the visible region o f the electrom agnetic spectrum.
hydrogen. W hat is the wavelength o f light that causes W hich electron transition causes the em ission of a
this excitation ? 973.5 A ° photon with a wavelength o f 6563 A°. 3->2

6.69 An electron in an orbit o f principle quantum

6.67 Energy o f 175 kcal/mol is required to ionize
num ber nj in a hydrogen atom makes a transition to a
gaseous magnesium atoms. Calculate the lowest fre­
orbit o f principle quantum number 4. During this tra-
quency o f light that can ionize a magnesium atom.
sition a photon with a w avelength of 4861 A° is ab­
1.8 3 x lO ISH z
sorbed. Calculate n;. 2
6.68 Electron falls from higher energy levels to
M odern A tom ic Th eo ry and Electron C onfig uration
6.70 Indicate each of the following for n=4 em it the greatest energy on returning to its ground
a) the num ber of subshells state ?
b) the total num ber of orbitals a) 1S22 p 1 b) 1Is„22s
u\ o„ 2-j
3p„2
c) the total number of electrons that can be held. c) ls 22 s 22p 5 d) ls 22s 23p 63d 3

6.71 The orbitals may be designated by letters 6.78 W hat is the atom ic num ber o f the each of
such as s, p, d, f, g ..... the following elem ents whose ground-state electron
a) the orbital g appears in which shell first ? configurations end with
b) how many g orbitals are there in this shell ? a) 2p 4 b )3 s 2 c) 3d 6 d) 4p 3

6.72 Discuss the sim ilarities and differences b e­ 6.79 Indicate the atomic num ber o f the elem ent in
tween a) Is and 2 s b) 2px and 2py which filling of the 4 d orbitals by electrons is com ­
pleted ? 4 8
6.73 Indicate which of the following electron con­
figurations are im possible and explain why they can 6.80 W rite the electron configurations o f each of
not be realized. the following ions.
a) lp 3 b) 3p& c) 3 s2 d) 2s2 e) 2d a) Mg2+ b) S2' c) Si4' d) Cl7+ e) Cr6+ f) As3'
12
f) 5d 2 g) 3f] h) 2p 4 and i) 3p 7
6.81 W hat is the atomic number of the atom that
6.74 W rite the ground state electron configura­ has 6 electrons in its 4lh energy level? 34
tions of the following atoms by using subshell desig­
nation and orbital diagram notation. 6.82 An atom has a configuration ending o f 4p3.
а) 3Ы b) 7N c) i0Ne d) 15P e) 35ВГ If it has nine less protons than its number o f neutrons,
0 53I g) бзЕи h) 42Md i) 79Au what is its mass number ? 75

6.75 How m any unpaired electrons are there in 6.83 X has 14 neutrons and has 1 electron in 3p
each of the following unexcited atoms ? orbital. W hat is the m olecular weight o f X 2S 3 ? 1 5 0 g
a) В b) S с) As d); Cr e) Hg and f) Eu
6.84 The elem ent Y has 3 electrons in 3p orbi­
6.76 Decide which of the following electron con­ tals. If 0.1 mol o f Y 2O 3 weighs 11 g, how many neu­
figurations are not allow ed by the Pauli exclusion trons does it have ? 16
principle. Explain why.
6.85 23 g of X02 gas occupy 5.6 L at 2 atm and
a) l s 22s 22p 4 b) ls 22s 22p 63s 3
0°C. If X has 3 electrons in 2p orbitals, how many
c) l s ^ p 1 d) l s 22 s 22 p 63s 23 p 10
neutrons does it have ? 7
6.77 Select the electron configurations that are
6.86 7/27 o f X2O5 by mass is X. If X atom has 7
not ground state configuration. W hich electron will
neutrons, write its electron configuration.
 Atomic Structure and Chemical Periodicity 237

Periodic Table and Periodic Properties

У 6.87 D efine A group and В group elem ents in found to be 0.6 M. If the neutral X atom has 14 neu­
terms of s, p, d subshells. trons on the nucleus, find its place in the Periodic
Table. 3r d period, IIIA grou p
6.88 W hat are the group and period numbers of
each of the following atoms? 6.100 Based on their positions in the periodic
a) n N a b) jзAl c) ieS d) 3 4 Se e) збКг table, select the atom with larger volume.
f) 39Y g) 37Rb h) 47Ag i) 52Te a) K, Cs b )M g , P c) Rb, О d )L i, Br

6.101 Explain why negative ions have larger,

6.89 Consider the elem ents that have the atomic
positive ions have smaller volumes than their parent
num bers 3, 8 , 11, 16, 18, 19, 33. W hich ones of
atoms.
these elements have similar chemical properties?
6.102 In each of the following pairs indicate the
6.90 Identify the groups that have the following
species that is smaller in size.
electron configurations in their valence shell.
a) K+, Ca2+ b) S2\ СГ c) Cl", K+
a) n s 1 b) ns2n p 3 c) ns 2np 6
d) Na+, K + e) I", Br" f) Fe2+, Fe3+
d )n s 2 (n -l)d 1 e ) n s 2 (n -l)d 3 f) ns 1 (n -l)d 10
6.103 Arrange each of the following groups in or­
6.91 Identify the location of each of the ions in
der of increasing energy to remove one electron :
the periodic table.
a) Na, Mg, Al b) Na+, Ne, СГ c) Fe, Fe2+, Fe3+
. a ) 15X 3- b) 20Y 2+ c ) 3iG a 3+
' 6.104 Explain why ionization energies decrease
6.92 X 2+ has 36 electrons, what is its place in the
from top to bottom in a group but increase from left
periodic table ?
to write across a period.
6.93 A 2- has 8 electron in its 3rd energy level.
6.105 W hich one o f the follow ing w ill have
What are the group and period number of A ?
higher first ionization energy ?
3 rd period,VIA group
a) B 5 or 6C b) 80 or 16S
6.94 W hat is the atom ic num ber of the element
c) i2Mg or 13A1 d) 15P or j 6S
which is in the 5lh period and IIIA group?

6.95 W hat is the atom ic num ber of the 4 th ele­ 6.106 How much energy is needed to convert 4.6
ment in group IIIA ? 49 g of sodium atoms to Na+ ions in the gaseous stale ?
(I l = 1 1 8 kcal/mol) 23.6 kcal
6.96 Oxygen (Z= 8 ) is the first m ember of the
VIA group. W hat is the atomic num ber of the third 6.107 Consider the elem ents : 5A, 7B, 9C, n D ,
elem ent in the same group ? 34 12E >

a) Arrange these elements in order of increasing

6.97 A 3" and B 1" have the sam e number of elec­ atomic sizes.
trons. If В is in the 2nd period and VIIA group, what b) Arrange them in order of increasing their first
is the place of A in the table ? ionization energies.
2nd period, VA group
c) Which one of them has the highest second ioni­
6.98 0.1 mol o f СаХг weighs 20 g. If X has 45 zation energy?
neutrons, what is the place of it in the table ? d) Which one of them has the highest third ioniza­
1h
4 period, VII A group
tion energy? д
6.99 W hen 21.3 g o f Х(Ж >з)з dissolve in water €pW hich ones of them metals and which ones are
to give 500 mL solution, the molarity o f N 0 3 is nonmetals ?
238 Chapter 6

0 W hat is the oxidation num ber of each atom in b) If possible, indicate the group num ber of each
its most stable state? element in the periodic table.
g) W rite the formulas of the compounds between c) W hich ones of these elem ents have sim ilar
the following pairs o f elements. (1)A and В (2)D and С chemical properties ?
(3)E and В d) If three of these elements are in the same period,
6.108 Consider these ionization energy data for which is on the left and which is on the right side of
the elements А, В, C, and D the period?
л e) Which one of the same group elements is at top
E le m en t It 12 I3 14
o f the group ?
A 190 370 1 1 1 0 1960
f) If one of these elements is a noble gas, which is
В 180 2400 2700 3100
it?
С 175 400 2800 3200

V. D 390 720 1 2 0 0 1800 J g) If possible write the formulas of the stable com­
pounds between these elements and 17C1.
a) How many valence electrons does each element - h) Which element has the most metallic character ?
have ? Why ?

SELF TEST
____ г I - tx
1. X and YTorm two different compounds X 2Y 3 sym bol
p ro p e rtv X3- 6Y R
and X 3Y 4. If the mass ratio of X to Y is 7/3 in X 2Y 3, •э- г
p ro to n no 7 ___
what is the mass ratio of X to Y in the second com ­ e le c tro n no T 10
a vM
pound.
m ass no 14 !T 16 28
A) 7/9 B) 11/7 C) 21/8 D) 25/4 E) 27/9 ato m ic no T Or 14

2. When 30 cm 3 of N 2O arc reacted with 40 cm 3 (n e u tro n noT 8 9 vM j

of O 2 10 cm 3 of N 2O remains behind. W hat is the ra­ Which of these species are isotopes of each other ?
tio between the combining volumes of gases ? A) L, R B) X,Y, R С) X, Y, L
A) 3/4 B) 3 /3 ; C) 1/3 D) 2/3 E) 1/2 D) X, L, R E) X, R

3. A current of i .34 A is passed through a solu­ 7. The energy difference between the two energy
tion, which contains X 1+ ions, for 10 hours and 54 g levels of an atom is 28.56 kcal/mol. W hat is the fre­
of X is deposited. W hat is the atomic weight of X ? quency of the light which is emitted when one mole of
A) 27 B) 54 C) 81 D) 108 E) 134 electrons falls from a higher shell to a lower shell ?
(h=9.54xl0 ' 14 kcals/mol)
4. Two solutions which contain C a2+ and Xn+ A) 2 .7 x l0 "12 В) ЗхЮ "14 С) 3 .3 x l0 ' 15
ions are clcctrolyzcd by using the same amount of D) ЗхЮ 14 E )4 .1 x l0 ' 13
electricity. If 2.4 g of Ca and 2.08 g of X arc deposit­
8. Which statement about Bohr's atomic model is
ed, w hat is the possible form ula of nitrate o f X ?
WRONG ?
(Ca=40, X=52)
A) Electrons rotate in circular orbits
A) XNO 3 B) X (N 0 3)2 C) X (N 0 3)3
B) If an atom gains or loses energy, electrons may
D) X (N 0 3)4 E) X2(N 0 3)3
change their orbits.
C) Each shell has a constant energy calculated by
5. The ion X3+ has 18 electrons. If it has 24 neu-
En= -313.6/n2 (kcal/mol)
trohs, which one of the following is isotopically relat­
D) Electrons can only exist in specific orbits
ed to the atom X?
around the nucleus.
A) 24X B) 2 j5X C) 2 ^X D ) 42X E) jgX
E) The number of subshclls in each shell is given
by the formula, n 2
 Atomic Structure and Chemical Periodicity 239

9. Given the following electron configurations. \ 16. W hich one o f the follow ing statem ents is
X : ls 22s 22p 63s 1 Z : ls 22s 22p 63s 23p 64 s 13d 5 WRONG, for these elements?
Y : 1s22s 23 s 1 L : ls 22s 22p 63s 23p 64s 23d 104p 3 A) A is in the 3rd period, IIA group of the periodic
W hich one o f the following statements is WRONG? table.
A) The atomic number of X is 11. B) A and E have similar chemical properties.
B) The electron configuration of Z is not written C) F is an alkali metal, С is a halogen.
correctly. D) А, В, E, F are metals C, D are nonmelals.
C) L5+ has 28 electrons. D) Y is an excited atom. E)The most stable ionic form o f the element E is E 2+
E) L has 3 unpaired electrons.
f 17) W hich o f the following statem ents is C O R­
10. W hich one of the following cannot be used to
RECT for these elements.
determine the place of an element in the periodic table?
A)E has the lowest first ionization energy.
Д) Number of protons 3 ) Atomic number B)F has the highest first ionization energy.
C) Mass number T>) Nuclear charge C)Thc first ionization energy of В is greater than
E) Number of electrons when it is neutral
that of C.
11. X O 3 (g) has a density of 2 g/L at 127°C and D)The first ionization energy o f A is smaller than
0.82 atm, and X2" has the same number of electrons as that of E
2oCa2+. How many neutrons docs X have ? 0= 16 E)E has the highest third ionization energy.
A) 12 B) 14 C) 16 D) 18 E) 20
/1 8 / Which one is the molecular weight in g/mol
12. W hich is the atomic number of the element in of the compound formed between j^X and 3f2Y ele­
the 3rd period, VIIA group ? ments?
A ) 17 B) 16 C) 15 D) 13 E) 12 A) 150 B) 123 C) 91 D) 86 E) 59

13. A 3" and B l + have the same number of elec- 19. Given the elements: П А, 12B ’ 13C. 19D -
11 >0 H
trons. If В is in the 3 period and IA group, which are I. A and D are in the same group.
the period and group numbers of the element A ? И. В has three valence electrons.
A) 2.P, VIIIA (В ) 2.P, VA "С) 2.P, VIIA III. All of them are metals.
D) З.РДНА E) 3.P, IVA IV. D has the strongest metallic character.
14. An ion XO^ has 50 electrons totally. If X Which ones of these statements are correct ?
atom is located in the 3rd period VA group of the peri­ A) I, II В) I, III С) I, II, IV D) I, III, IV E) I, II, III
odic table which one is the value o f a in the formula
20. Answer the 20th question according to the ele­
XO^ ? ments in the periodic table given below.
A) 3+ B )3 - C) 2+ D) 2- E) 0 ГГ yfi I—
/ ^ G i v e n the balanced equation : MR
/
X2O 3 (s) + 6 NaOH (aq) -» 2Na 3X 0 3 (aq) + ЗН 2О (1) X z L T
If 3.06 g of X 2O 3 completely reacts with 600 mL of
0.3 M NaOH, and X contains 14 neutrons, which one Y
is the period and group number of X in the periodic 1
table ? 0 = 1 6 Which one Of the following statements is WRONG?
, A) 3rd period IIIA group B) 3rd period IVA group A) The formula of the compound between Y and M
C) 4th period VIIIB group D) 2nd period IIIA group is YM.
E) 2nd period, IIIA group (§) The electron configuration of L ends with 4p4.
C) Y has stronger metallic properties than X.
D ata for questions 16 and 17. i 2A, gB, 9C, 10D, D) The formula of compound between Z and M is
ZM 3.
20E > 11F -
E) T may have the oxidation numbers 2- and 6+.
 >; ■■■■■■

CHAPTER 111

Some Selected Families in the

Periodic Table

The objectives of this chapter are to enable the student to :

1. Practice the periodic properties.
2. Describe the physical and chemical properties of noble
gases.
3. Recognize the occurrence of the noble gases.
4. Describe the alkali metals : their physical and chemical
properties; and their occurrence and preparations.
5. Describe the halogens : their physical and chemical prop­
erties; and their occurrence and preparations.
 Some Selected Families In The Periodic Table 243

7.1 PERIODIC PROPERTIES

W e have discussed the general features o f the periodic table in the previ­
ous chapter. N ow w e w ill exam ine the detailed chemistry o f the elem ents in
specific groups ; the noble gases, the alkali m etals, and the halogens. W e shall
find that there are very marked resemblances among the properties o f the same
group elem ents.

7.2 NOBLE GASES

The elem ents in group 0 (or V IIIA) are know n as the noble gases. The
noble gases are H e, N e, A r , K r , X e, and R n . AIJ a re c o lo rle ss m o n a to m ic
gases a t room tem peratures.
A ll o f the noble gases except helium are obtained by careful distillation o f
liquefied air. H elium occurs in underground pockets, how ever, often m ixed
with natural gas.
H elium is w id ely used in an "artifical" air m ixture necessary in
deep-sea diving. It is also w idely used in weather balloons. N eon
; He is used in fam iliar electric sign s know n as n eon signs. A rgon is the
Ne
Ar m o st abundant o f the noble gases in the atm osphere. It is used to fill
Kr
Xe electric light bulbs. Argon greatly increases the life o f the glow in g fila­
Rn
m ent o f the bulb. Radon is given o ff from the radioactive elem ent radi­
um and is itse lf radioactive. Radon is used as a source o f a particles in
cancer therapy.
The properties o f the noble gases reflect their very stable electronic con­
figurations. Som e o f their properties are listed in Table 7.1

T A B L E 7.1 S o m e P roperties o f T he N o b le G ases

N
G as A tom ic V a len c e shell M elting B o ilin g F irs t io n iz a tio n A to m ic
n u m b er c o n fig u ra tio n s P oint ( ° C ) p o in t(° C ) e n e rg y (k c al/m o l) radius(A °)

He 2 Is 2 -272.2 (at 26 atm) -268.9 566 0.93

Ne 10 2s 2 2 p6 -248.6 -245.9 497 1.31

Ar 18 3s2 3p 6 -189.3 -185.8 363 1.74

Kr 36 4s 2 4p 6 -157 -152.9 323 1.89

■Уг»:.'";
Xe 54 5s2 5p6 -112 -107 280 2.09
°y

86 6 s2 6p 6 -71 -61.8 248 2.14

a

The noble gases have no tendency to com bine w ith each other to form
m olecules. With the exception o f helium , a ll o f these elem ents h a ve fille d o u t­
e r p orbitals. The filled outer subshell represents a state o f high stability.
U ntil 1962 it w as thought that the n ob le g a ses form ed no ch em ical-
com pounds. T he first xenon com pound was m ade using platinum hexafluo-
ride, PtF6. This substance reacts w ith xenon to form XcPtF6. It is now know n
that xenon w ill com bine directly w ith fluorine as fo llo w s to g iv e three xenon
fluorides:
244 Chapter 7

Xe + F 2 = ;X eF ,
Xe +2 F 2 £ • XcF 4
Xe + 3F 2 £ : XeFfi
T h ese co m p o u n d s are all solids at room tem p eratu re. A ll o f th e se com p o u n d s
can be stored in glass containers, b u t they react w ith w ater to give a n u m b er o f
d ifferen t o x y g en and hyd ro g en -co n tain in g com pounds.
XeF 6 (s) + H20 (1) -> XeO F 4 (1) + 2HF (g)
C om plete reaction o f X eF 6 o r X eO F 4 produces solid X e 0 3 :
XeF 6 (s) + 3H20 (1) -> X e 0 3 (aq) + 6 HF (aq)
XeOF 4 (1) + 2H20 (1) -> X e 0 3 (aq) + 4HF (aq)
N o co m p o u n d s w ith H e, N e, o r A r h av e yet been reported.
7.3 ALKALI METALS
T h e a l k a li m e ta ls , lith iu m , s o d iu m , p o ta s s iu m , r u b i d i u m ,
c e s iu m and f r a n c iu m , are the m e m b ers o f G ro u p IA . T h e electro n ic
mM
co n fig u ratio n o f each o f the alkali m etals is th at o f the p reced in g noble
t' ■ ■ >1 gas p lu s a single s v alence electron in the o u te r shell. T he elem ents are
adi I ■■■
ЫЛ ■ ■ i. ■ ■ d I ■ ■ I »■ s ilv e r y m e ta ls and are c o m p a r a tiv e ly so ft (th ey c a n be cu t by a
|4Л ■ I ■ m Mm ■ ■ ■я ■
- Л I I ■ 1I I lb k n ife ). T h e y are s o lid s a t r o o m t e m p e r a t u r e . T h e alk a li m e ta ls
Я h a v e lo w m e ltin g a n d b o ilin g p o in ts . S ee T a b le 7 .2 . M e ltin g
point, b o ilin g point, and h ardness increase w ith increasing atom ic n u m ­
ber. T h e y also h a v e lo w d e n s itie s in co m p ariso n w ith o th e r m etals.

T A B L E 7.2 S o m e P ro p erties o f A lk a li M etals

---------------------------------
L ith iu m S o d iu m P o ta ssiu m R ubidum C e siu m

atomic number 3 11 19 37 55
outer electron config. 2s 1 3 s1 4 s1 5s 1 6s 1
atomic radius (A”) 1.23 1.57 2.03 2.16 2.35
j ionic radius, M+ , (A°) 0.60 0.95 1.33 1.48 1.69
melting point (°C) 179 97.5 63.7 39.0 28.5
j boiling point f C ) 1336 880 760 700 670
I density (g/cm3) 0.53 0.97 0.86 1.53 1.96
I first ionization energy 124 118 100 96 90
: (kcal/mol) f
V 1 J
W h en alkali m etals and th e ir c o m p o u n d s are stro n g ly h eated in a flam e,
T A B L E 7.3 F l a m e C o ­ they g iv e ch aracteristic b rig h t colors to the flam e. S ee T ab le 7.3. T h ese bun-
lors o f a lk a li m etals sen b u rn e r co lo rs serve as the basis fo r id entifying th ese elem en ts in spectral
analysis.
Metal Color
7.3.1 OCCURRENCE AND P R E P A R A T IO N
G ro u p IA m e tals o r the a lk a li m e ta ls , c o n stitu te th e m o st re a c tiv e
g ro u p o f m etals. T h ey h av e th e sm allest io n iza tio n e n erg ie s in eac h period.
A s expected, n one o f the alkali m etals is fo u n d fr e e in nature because o f their
very high reactivity. T h e lo ss o f one electro n b y an alkali m etal atom results
 Some Selected Families In The Periodic Table 245

in the electron configuration o f a noble gas. T h erefore these elem ents alw ays
o ccur in chem ical com bination as 1+ ions. W ith a few exceptions, alkali m etal
com p o u n d s are ionic. The reactivity o f alkali m eta ls increases w ith increasing
atom ic num ber. T herefo re, in m o st cases cesium is the m o st reactive clem en t
o f the group and lithium is the least reactive.
T h e alkali m etals are o fte n found in n atu re as ions in aq u eo u s solution,
prim arily in sea w ater and in deep brine w ells. T h e m o st abundant o f the alkali
m etals are sodium and potassium .T here are also large underground deposits o f
salt and so m e surface d eposits in dry salt lak es.T h e alkali m eta ls c o m m o n ly
o ccu r as chlorides in large salt deposits that w ere form ed by the evaporation o f
ancient seas. Som e inland seas contain m u ch hig h er con cen tratio n s o f sodium
O x id a tio n m e a n s lo ss o f chlo rid e. W hen an inland sea evap o rates, the lea st soluble salts are d eposited
e le ctro n s, re d u c tio n m eans
first.
g a in o f e le c tro n s.
Since alkali elem en ts o c cu r ex clu siv ely in th e form o f the M + ions (M +
represents alkali ions), these ions m u st b e reduced in o rd e r to prepare the ele ­
m ents. F o r m an y years sodium w as obtained by red u cin g so d iu m carb o n ate
w ith carbon at a high tem perature.
N a 2C 0 3 (s) + 2C (s) — > 2Na (1) + 3CO (g)
T oday sodium is obtained by electrolysis o f m olten sodium chloride.
Na+ + ё — > Na
P otassium can be obtained by electrolysis o f m o lten potassium chloride, b u t it
is nearly all m ade using sodium as the reducing agent:
KC1 (1) + Na (1) ---- > NaCl (1) + К (s)

E X A M P L E 7.1 Calculations Based on Alkali Metals

Problem: How many liters o f CO gas at 0°C and 2 atm can be obtained from 200 g-samplc of Na 2C 0 3 which
is 26.5% pure by mass ? N a 2C 0 3 (s) + 2C (s) -» 2Na (l) + 3CO (g)

Solution : The am ount o f pure Na 2C 0 3 in the sample is : 200 x = 53.0 g => n = -3..&—_ = 0.5 mol
100 106 g/mol

The equation for the production of CO from N a 2C 0 3,

Na 2C 0 3 (s) + 2C(s) -> 2Na (1) + 3CO (g)
1 mol 3 mol
} x = 1.5 mol o f CO
0.5 mol _______________ x_____

The volume of CO : PV = nRT o rV = L5 x ° :M 2 x 271 = 16.8 L

7.3.2 C O M P O U N D S AND R E A C TIO N S OF

A LK ALI M ETALS
T h e alkali m etals are the m o st reactiv e o f all the m etals. W h e n t h e y a r e
p l a c e d in w a te r , th e y r e a c t v io le n tly , r e le a s in g h yd ro g en a n d f o r m i n g th e
h y d r o x id e o f th e m e ta ls .
2M (s) + 2H20 (1) -> 2M+ (aq) + 20FT (aq) + H 2 (g)
A ll o f th e m etals react rapidly w ith o x ygen w h en th ey are ex p o sed to air. T he
246 Chapter 7

p ro d u cts o f the reactions d iffe r fo r the d ifferen t m etals. L ithium reacts to give
a "norm al" oxide containing the O 2- ion.
4Li + 0 2 —i 2Li20
S o d iu m reacts w ith oxy g en to form a peroxide th at co n tain s th e 0^~ io n
2Na + 0 2 -> Na 20 2 (sodium peroxide)
T h e o th e r alkali m etals form superoxides th a t co ntain the 0 2 io n
К + 0 2 —> K 0 2 potassium superoxide
Rb + 0 2 —» R b 0 2 rubidium superoxide
Cs + 0 2 -» C s 0 2 cesium superoxide
W h en lith iu m oxide o r any o f the o th er n orm al o x ides reacts w ith w ater, a h y ­
d ro x id e o f m etal is form ed.
Li20 + H20 -> 2LiOH
Sodium peroxide reacts w ith w ater to give hydrogen peroxide
Na 20 2 + 2H20 -» 2NaOH + H 20 2
T h e superoxides react w ith w ater to produce oxygen
2 K 0 2 + 2H20 2KOH + 0 2 + H 20 2
T h e d irect actio n o f a h alo g en (X 2) on th e alkali m etal (M ) results in an alkali
m etal halide.
2M (s) + X 2 (g) -» 2MX (s)
F o r exam ple,
2K (s) + Br 2 (1) -> 2KBr (s)
Lithium is the only alkali m etal w hich reacts directly w ith nitrogen gas. T h e re ­
action is carried o u t by heating the elem ent in nitrogen.
6Li + N 2 -> 2Li3N
T his m etal nitride reacts w ith w ater to form N H 3 (g) and the m etal hydroxide.
L i3N (s) + 3H20 (1) -> NH 3 (aq)+ 3LiOH (aq)
Ionic h ydrides are produced by the reaction o f the alkali m etals w ith hyd ro g en
gas. In these co m p o u n d s the h y d ro g e n ex ists as h y d r id e ion H '
2M (s) + H 2 (g) —> 2MH (s) (where M = an alkali metal)
P o ta ssiu m and sodium ca rb o n ates h av e b een k n o w n sin ce v e ry e arly tim es.
P o tassiu m carbonate, K 2C 0 3, w as obtained from the ashes le ft afte r the b u rn ­
in g o f w ood and o th e r land plants. S odium carb o n ate, N a 2C 0 3, w as o b ­
tained from the ashes left after the burning o f sea-w eed. S odium carbonate is a
C o m m o n so d iu m c o m ­ very im p o rtan t industrial chem ical, w h ich is used in the m an u factu re o f glass,
p o u n d s: pap er, d eterg en ts, and soap. In the h o m e it is used fo r w ash in g , fo r clean in g ,
N aC l - T ab le salt and fo r so ftening "hard" w ater. T o m eet the en orm ous need, sodium carbonate
N а 2 СС>з. 10 H 2 O -W ashing w as also m a d e fro m lim e sto n e and so d iu m c h lo rid e b y th e solvay pro­
so d a
cess.
NaHCC> 3 -B aking powdcjr
C a C 0 3 (s) + 2NaCl (aq) — > Na 2C 0 3 (aq) + CaCl2 (aq)
N aO H -C austic soda
R e c e n tly , n e w sou rces and n ew m ethods h av e b e e n fo u n d to o b ta in sodium
N a 2S 2O 3 .5 H 2 0 -
carbonate.
P h o to g ra p h e r's h y p o .
Som e o f the com m on reactions o f IA m etals are sum m arized in T ab le 7.4
 Some Selected Families In The Periodic Table 247

T A B L E 7.4 R e a c tio n s o f A lk a li M e ta ls

( R eaction R em arks ^
2M + X 2 —> 2M X X 2 = all halogens
4L i + 0 2 —^ 2 L i20 e x c e ss o x y g e n
2 N a + C>2 —^ N a 20 2

M + o 2 -> m o 2 M = K , Rb, Cs
2M + S - » M 2S also w ith Sc and Т е
6 Li + N 2 —> 2 L i3N Li o n ly
12M + P 4 —> 4 M 3P also w ith A s, Sb
2M + H 2 —> 2M H
2M + 2 H 20 2M O H + H 2 at ro o m tem p e ra tu re
2M + 2 H + - » 2 M + + H 2 v io le n t re a c tio n
V J

B ecause they have very low m elting points and excellent ability to co n ­
duct heat, sodium and potassium in the form o f alloy w hich is a liquid at room
conditio n s, are used as cooling agents in n u c lear reactors.
S odium v a p o r lam p s are used to lig h t foggy sections o f h ighw ays. S o d i­
um v ap o r produces an intense yellow light.

E X A M P L E 7.2 C a lc u la tio n s B a se d o n A lk a li M e ta ls
Problem : 2.24 L o f hydrogen gas (at STP) is produced by the reaction of 7.8 g of an alkalimetal with w a­
ter. If the metal is in the 4lh period, how many neutrons does it have in its nucleus?
Solution : The reaction for the production of H2 from alkali metals:
M + H20 -> MOH + 1/2H2
1 mol of M produces 11.2 L of H 2 at STP and therefore 2.24 L of H 2 is produced by the reaction o f 0.2 mol
of M.
The atomic weight of M = 7.8/0.2 = 39 g.
Since it is an alkali in the 4th period, its configuration ends with 4 s 1 or M: Is 2 2s 2 2p 6 3s 2 3p 6 4 s 1. So the
number of its protons is 19, and the number of its neutrons is 39-19=20.
1 ■ ------------------------------------------------------------------------------

EXERCISE 7.1 How many gram s of C aC O j, which is 70% pure by mass, are required to obtain 200g of
N a 2C 0 3, 79.5% pure by mass, by solvay process? 214.3 я

7.4 HALOGENS
A ll o f the elem en ts in g ro u p V IIA o f the p erio d ic tab le are no n -
m etals. T h e ir n am e, h a lo g e n , m ean s salt form er. S o m e p ro p e rtie s o f
the halogens are sum m arized in T ab le 7.5
T he p u r e elem ents ex ist as dia to m ic m o lecu le s in w h ic h the a tom s
a re h e ld to g e th er by a c o v a le n t bond. F lu o rin e (F 2) and ch lo rin e (C l2)
are gases at room tem perature. B rom ine (Br^) is liq u id , and io d in e (I2)
is solid. In the elem ental states o f the h alo g en s th e y are toxic and d a n ­
g e ro u s substances. T h e d a n g e r decreases as the ato m ic n u m b e r o f the
halogen increases.
248 Chapter 7

T A B L E 7.5 So m e P roperties o f the H a lo g en s

Property Fluorine Chlorine Bromine Iodine

Color light yellow yellowish green reddish brown violet black
I Atomic number 9 17 35 53
Valence shell 2 s 22 p 5 3s23p 5 4 s 24p 5 5s25p 5
M elting point (°C) -218 -101 -7 +113
Boiling point (°C) -188 -35 +59 +183
Atomic radius (°A) 0.72 0.99 1.14 1.33
Ionic radius (°C) 1.36 1.81 1.95 2.16
I.IE (kcal/mol) 402 300 273 241
.Electron affinity 79.5 83.3 77.5 70.6 J
T h e in term o lccu lar attractions increase as the sizes o f halo g en s increase.
T h e re fo re, io d in e has the h ig h e st m eltin g and b o ilin g p o in t, flu o rin e has the
lo w est m e ltin g and boiling points. See F igure 7.1.
T h e h a lo g e n o f each perio d h as a h ig h io n iza tio n energy, second o n ly to
th a t o f th e n o b le gas o f the period. Io n izatio n en erg ies decrease w ith in c re a s­
ing atom ic radius, from fluorine to iodine.

7.4.1 O C C U R R E N C E A ND P R E P A R A T IO N
T h e h alogens are very reactive elem en ts, so th a t th ey do n o t o ccu r
free in n atu re. T h e y m u st be o b ta in ed from h a lo g e n -c o n ta in in g c o m ­
p o u n d s.
F lu o rin e
T h e m ain source o f flu o rin e is th e m in eral f lu o r s p a r , C a F 2. T his
su b sta n c e is treated w ith co n ce n tra ted H 2S 0 4 to m ak e H F th a t is the
o n ly acid affecting glass.
S i 0 2 (s) + 4 H F (aq) -> S iF 4 (g) + 2H 20
E le m e n tal flu orine is p repared b y electro ly sis o f m o lten K H F 2, to
w h ic h an e x cess o f H F is ad ded as e le c tro ly te . S om e flu o rin e c o m ­
FIGURE 7.1 T h e b o ilin g p o in ts p ounds are able to w ithstand to o th -decaying acids. T h e flu oride ion can
o f h a lo g e n s in c r e a s e w ith in ­
be supplied in drinking w ater. It can also be pro v id ed in toothpaste o r in
c rea sin g a to m ic n u m b er.
sjxecial solutions that can be applied by a dentist.
C h lo rin e
C hlo rin e o ccu rs m o stly as th e ch lo rid e ion, C l ' , in se aw ater and in d e ­
p o sits o f sodium ch loride (N aC l) and p o tassiu m ch lo rid e (KC1). T h ese c h lo ­
rid es h a v e b e e n fo rm ed by the ev ap o ratio n o f a n c ie n t seas. C h lo rin e is the
m o st ab u n d an t o f the halogens.
C hlorine is produced com m ercially from sodium chloride by the electro l­
ysis o f m olten salt o r by the electrolysis o f concentrated solutions o f salt.
2NaCl (aq) + 2H20 (l) —> C l 2 (g) + H 2 (g) + 2NaOH (aq)
T h e p rin cip al uses o f ch lorine are the ch lorination o f d rinking w ater, the
m anufacture o f m any industrial chem icals, and the production o f chlorine b lea­
ches.
 S o m e S e le c t e d F a m i l i e s I n T h e P e r i o d i c T a b l e 2 49

B r o m in e
T h e com m ercial source o f brom ine is seaw ater. M etal b rom ides o c c u r in
sm all q u an tities in seaw ater. B rom ine is also found in salt deposits. T o o b tain
brom ine, the w ater is first acidified and then saturated w ith C l 2 to carry o u t the
reaction.
Cl 2 (g) + 2Br- (aq) Br 2 (1) + 2СГ (aq)
O ne o f the m o st im portant uses o f brom ine is fo r the m an u factu re o f b ro ­
m in e co m p o u n d s. B rom ine co m p o u n d s are u sed fo r gaso lin e ad d itiv es, p e sti­
cides, treatin g p lastic m aterials and tex tiles, the m a n u fa ctu re o f ph o to g rap h ic
film .
I o d in e
Io d ine com es from three m ain sources; seaw eed, salt b rin es, sodium io-
date, N a I 0 3, found in larg e dep o sits in C hile. S o lu tio n s co n tain in g the iodate
ion are reduced w ith hydrogen sulfite ion:
210' + 5H SO ' 3HSO 4 + 2SO ^'+ I 2 + H20
Io d in e does n o t h av e as m any im p o rtan t u ses as the o th e r h alogens. S il­
v er iodide is used in the m anufacture o f photographic film . A dilute solution o f
io d in e in aq ueous alco h o l, c alled tin c tu r e o f io d in e , is a co m m o n a n tise p ­
tic. T h e b ody has to have the iodide ion in the diet. W hen iodide ion is m issing
from the d iet fo r an ex tended p erio d , a large sw ellin g -a goiter- can d ev elo p
in the neck.

E X A M P L E 7.3 E le c tr o ly s is o f S o d iu m C h lo r id e
Problem'. How many liters o f chlorine, Cl2, at STP arc produced by the electrolysis of 1M of 2 L sodium
chloride solution, NaCl? How many liters of 0.4 M NaOH solution arc obtained ?
Solution : The equation for the electrolysis of NaCl solution,
2 NaCl (aq) + 2H20 (1) -----> Cl2 (g) + H2 (g) + 2NaOH (aq)
2 mol of NaCl ( n=MxV = 1x2=2 mol) give 1 mol of Cl 2 gas and 2 mol of NaOH
The volume o f 1 mol o f Cl 2 gas at STP is 22.4 L

The volume of 0.4 M NaOH solution, V = — = ? mo1 = 5 L

__________________________________________ M 0.4 M_________________________________________________

7.4.2 CH EM ICA L PR O PER TIES

T h e h a lo g e n s co m b in e w ith m e tals and n o n m c ta ls and a m o n g th e m ­
selves. S om e reactions o f the halogens are sum m arized in T ab le 7.6
T A B L E 7.6 S o m e R e a c tio n s o f the H a lo g en s ( X2= F 2, Cl2, B r 2, I2)
' G eneral R eaction R em arks л
nX 2 + 2 M -» 2 M Xn F 2 , C l 2 w ith p ra ctic a lly all m etals; B r2 , I2 w ith all e x c e p t n o b le m etals.
X 2 + H 2 —» 2H X
3 X 2 + 2P —» 2P X 3 w ith ex ce ss P; sim ilar re ac tio n s w ith As, Sb, and Bi
5 X 2 + 2P -» 2PX 5 w ith e x ce ss X 2 , but not w ith I2 ; S b F s, S b C ls, ASF 5 , ASCI 5 , and B iF s
m ay be sim ilarly p re p are d
X 2 + 2S —> S2X 2 w ith C l2 , B r 2
X 2 + h 2o H + + x - + HO X n o t w ith F 2
2 X 2 + 2H 20 -> 4 H + + 4X" + 0 2 F 2 rap id ly ; C l2, B r 2 slo w ly in su n lig h t
X 2 + H 2S - » 2H X + S
X 2 + CO —» c o x 2 C l2 , B r 2
x 2 + БОг s o 2x 2 F 2 , C l2
X 2 + 2 X " -> X ’2 + 2 X ' F 2 > C l 2 > B r 2 > 12
X 2 + X '2 -> 2X X ' fo rm atio n o f the in te rh alo g c n co m p o u n d s (all e x ce p t IF ) ^
 In com bin atio n w ith m etals the halogens alw ays have (1-) as an oxidation
n u m b e r and are called h alid es. T h e h alid es o f m etals h a v e h ig h io n ic c h arac­
ter.
H y d r o g e n h a lid e s
H y d ro g en reacts w ith each o f the h a lo g en s p ro d u c in g the h y d ro g en h a ­
lid es: H F , H C I, H B r, and H I.
H 2 (g) + X 2 —> 2HX (X 2 represents the halogens)
E xam ples,
H 2 (g) + F 2 (g) —» 2HF (g) (violent under all conditions)
H 2 (g) + Cl 2 (g) 2HC1 (g) (slow in the dark, explosive in sunlight)
T h e reactiv ity o f th e h alo g e n s w ith h y d ro g e n d ecreases from flu o rin e to
iodine.
In the lab o rato ry H F and H CI are m ade by p lacing m etal halides in w arm
concentrated sulfuric acid.
2MX (s) + H 2S 0 4 (1) -> M 2S 0 4 (s) + 2HX (g)
E xam ple,
2NaCl (s) + H 2S 0 4 -> Na 2S 0 4 (s) + 2HC1 (g)
H y d ro g e n b ro m id e, H B r, and h y d ro g e n io d id e , H I, can be m ad e u sin g
phosphoric acid instead o f sulfuric acid
3MX (s) + H 3P 0 4 (1) 3HX (g) + M 3P 0 4 (s)
E xam ple,
N al (s) + H 3P 0 4 (1) -> HI (g) + NaH 2P 0 4 (s)
T h e h y d ro g e n h alid es can also be p rep a re d b y the h y d ro ly sis o f p h o s­
phorus trihalide
PX 3 + 3H20 -> 3HX (g) + H 3P 0 3 (aq)
Exam ple,
PC13 (g) + 3H20 (1) -+ H 3P 0 3 (1) + 3HC1 (g)
A ll h y drogen halides are v ery soluble in w ater; w a te r solutions are called
h y d r o h a lic a c id s.
H F (aq)= hydro fluoric acid(w eak a cid ),H Q (a q )= h y d ro c h lo ric acid(strong)
H B r (aq )= h y d robrom ic acid (strong), HI (aq )= h y d ro io d ic acid(strong)
H y d ro flu o ric acid c an n o t b e k ep t in g lass b o ttle s b e ca u se it d isso lv e s
glass by the reaction :
4HF (aq) + S i0 2 (s) -+ 2H20 + SiF 4 (g)
M eta l h a lid e s
M etal halides can b e prepared by direct interaction o f the elem ents. Som e
typical reactions are given below :
2Na (s) + Cl 2 (g) -> 2NaCl (s)
Ca (s) + Br 2 (1) -> CaBr 2 (s)
Mg (s) + Cl 2 (g) M gCl 2 (s)
M etal h alid es c an also b e p re p ared by the reactions o f th e h y d ro g en h a ­
lides w ith h y d ro x id es, ox id es o r carbonates.
252 Chapter 7

SOM E NEW TERM S

Alkali m etals are the elem ents o f Group IA, ex­ Periodic law refers to the periodic recurrence of
cept hydrogen. certain physical and chemical properties when the ele­
H alogens are the elements o f Group VIIA; fluo­ ments are considered in terms o f increasing atomic
rine, chlorine, bromine, iodine, and astatine. number.
N oble gases are the elem ents o f G roup О (or Solvay process is a process that is used to pre­
VIIIA); helium, neon, argon, krypton, xenon, and ra­ pare Na 2C 0 3 from NaCl, C 0 2 and NH3.
don.

R E V IE W Q U E S T IO N S

7.1 W hy is it im portant to look for sim ilarities 7.8 Complete and balance each of the following
and differences among the chemical and physical prop­ equations. If no reaction occurs, write NR (refers to no
erties of elements ? reaction)
a) Cl 2 + KI (aq) -> b) I 2 + NaCl (aq)-+
7.2 Refer to the periodic table and identify the fol­ c) Br 2 + N al (aq) -> d) F 2 + H20 (1)
lowing
a) The element in Group IIIA and in the fifth peri­ 7.9 If you are given colorless aqueous solutions of
od. a chloride, a bromide, and an iodide, explain how you
b) An elem ent that has properties similar to those could identify each solution. W rite balanced equations
of sulfur. for the reactions ? / /
c) A very reactive metal in the sixth period.
7.10 W hy does the reactivity of the alkali m etals/
d) The halogen in the fifth period.
increase with increasing atomic number ?
e) The alkaline earth metal in the fourth period.
7.11 Com plete and balance the following equa­
7.3 Write balanced equations for the following re­
tions.
actions (if any)
a) К (s) + Br 2 (s) -+ b) Li (s) + 0 2 (g)
a) Magnesium with steam b) Sulfur with hydrogen
c) Na (s) + H 2 (g) -+ d) LiH (s) + H20 (1) -+
c) Sodium with iodine d) Potassium with water
e) К (s) + H20 (1) -+
e) Hydrogen with chlorine f) Neon with water

7.4 Predict the form ulas of chlorides formed by 7.12 Why have scientists found it convenient to
elements in Group IIIA of the periodic table. use reactions o f elements with oxygen and water to
help in grouping elements together in families ?
7.5 Elements A, X, Y, and Z form fluorides AF2,
X F4, YF4, and ZF. In which groups of the periodic 7.13 List two reasons why it is im portant for al­
table do you expect to find the elements A, X, Y, and kali metals to be stored under oil.
Z?
7.14 W hich o f the following is not a correct for­
7.6 Compare the following properties of francium mula for a substance at normal laboratory conditions ?
with the other alkali metals. Explain the reasons for your choices.
a) Ionic radius b) Oxidation state a) H 2S, b) CaCl2, c) He,
c) First ionization energy d) Melting point d) NaHe, e) A120 3, f) SiCl 3
e) Metallic properties
7.15 A certain metal, M, reacts with brom ine to
7.7 Explain why the ionization energy of helium form the compound MBr3. Predict the formula of the
is higher than that of any other neutral atom. oxide formed when M reacts with oxygen.
 Some Selected Families In The Periodic Table 253

7.16 A certain nonm ctal, Y, reacts with calcium c) reacts readily with elem ent ( Z = ll) to form an
to form the compound CaY, predict the formula of the ionic solid.
compound formed when Y reacts with lithium. d) has the highest ionization energy o f any element
in the family
7.17 W hy are gold and platinum called "noble
Elem ent B:
metals" ? Are the alkali metals also considered to be a) is a good conductor of electricity
"noble" metals ? Explain. b) melts at a temperature a few degrees above 25°C
7.18 Describe the relationships between the melt­ c) has a low ionization energy
ing points, boiling points, and atom ic numbers for 7.20 The metals of the second column o f the Peri­
each of the following families of elements. odic Table combine with the halogens to form ionic
a) The alkali metals b) The halogens solids. Write a general equation to represent these reac­
c) The noble gases tions using M for the metals and X for the halogens.

7.19 From the follow ing experim ental inform a­ 7.21 The m etallic elem ents Na, M g, and Si in
tion, identify which chem ical family and which ele­ row 3 o f the Periodic Table have atomic radii of 1.9,
ment is described. Answer each part separately. Identi­ 1.60, and 1.3 A°. Estimate the size o f aluminum atom
fy the specific element as soon as possible. in a metal sample.
Elem ent A:
7.22 The size of an atom can be expressed as the
a) has an ionization energy of more than 400 kcal/
closest distance o f approach by another atom. For the
mol
halogens the values are F, 1.35; Cl, 1.80; and Br, 1.95
b) is a gas at room temperature
A0. Estimate the value for iodine.

R E V IE W PROBLEMS
7.23 W hen 9.2 g of a mixture o f Na and Fe m et­ 7.26 Calculate the percent content (by m ass) o f
als are placed in H20 , 2.24 liters of H 2 gas at STP are xenon in the com pound X ePtF6. 29.8%
produced. W hat is the percentage of iron (Fe) in the
m ixture? 50% 7.27 How many kilograms o f sodium chloride are
required to produce 1450 kg o f chlorine by electroly­
7.24 How many liters o f air are required to bum sis? 2389 kg NaCl
10 L of a mixture whose percentage com position by
volume is 40 % helium, He; 20 % carbon monoxide, 7.28 How m any gram s o f hydrochloric acid
CO, and 40 % hydrogen, H 2. 15 L (HC1), 29.2 % by mass, are needed to obtain 13.44 li­
ters o f chlorine (Cl2) gas at STP by the reaction:
7.25 A precipitate of silver chloride, AgCl, with M n 0 2 + HC1 —> M nCl 2 + Cl2 + H20 (unbalanced)
a mass o f 4.305 g is obtained from a mixture of KC1 300 g
and NaCl with a total mass of 1.915 g. Calculate the 7.29 How many gram s o f silicon dioxide, S i0 2,
percentage com position (by mass) of the KC1 and would react with 500 mL o f 1 M HF to produce SiF4?
NaCl in the m ixture. 3 8 . 9 % К С 1,6 1 . 1 % N a C l 7 .5 g
254 Chapter 7

SELF TEST

1. W hich one o f the following is TRUE for IA A) I, III, IV В) II, III, IV С) III, IV
group elements? D) I, IV E) I, II, III, IV
A) Their number of valence electrons increase with
5. X 3+ : Is 2 2s 2 2p 6 3s 2 3p 4
increasing atomic numbers.
Y 2' : Is 2 2s 2 2p 6 3s2 Зр 1
B) Their first ionization energies decrease with in­
Z 1+ : Is 2 2s2 2p 6
creasing atomic number.
T 3- : Is 2 2s 2 2p 6 3s 2 3p 2
C) Their atomic volumes decrease with increasing
Which ones of these elements are the alkali metals?
atomic number.
A) X and Y B) Y and Z С) X, Y, Z
D) Their metallic properties decrease with increas­
D) Y, Z, T E) all
ing atomic numbers.
E) They exist as free elements in nature. (tT^Vhen 10 g of an alloy of sodium and mercury
is reacted with water, 2.24 L of hydrogen gas at STP
r2..AVhich o f the following is INCORRECT for
is evolved. W hat is the percentage o f Hg in the m ix­
the halogens from fluorine through astatine?
ture ? (Hg doesn’t react with water)
A) all have high ionization energy
B) all form a volatile, covalent hydride HX in A) 78 B) 42 C) 36 D) 54 E) 22
which the halogen X is exhibiting an oxidation state 7. Which of the following is IMPOSSIBLE ?
of 1+ A) 2NaCl + Br2 2NaBr + Cl 2
C) exist as discrete covalent molecules, F2, Cl2, "B) 2KBr + F 2 2KF + Br2
Br2, and I2 C) 2NaI + Cl2 -> 2NaCl + I2
D) show variable oxidation states of 1-, 1+, 3+, D) 2NaBr + Cl2 -> 2NaCl + Br 2
5+, 7+ in their various compounds E) 2NaI + Br 2 -> 2NaBr + I2
E) have an electronic configuration having one less
electron than the adjacent nobel gas. ^ j 0 .8 g of hydrogen is introduced into a 11.2 liter
( § j W hich o f the follow ing is INCORRECT for container which has chlorine gas at STP. The gases
the noble gases, from helium through xenon ? They react to form HCI gas. W hat will be the pressure in
the container after the reaction is completed at 0°C ?
A) have very low melting and boiling points.
A) 0.9 B) 1.8 C) 2.4 D) 3.2 E) 4.8
B) are monatomic.
C) have an outer shell electronic configuration
9. W hich one of the following reactions is
ns 2np 6 (except helium).
IMPOSSIBLE for potassium ?
$ ) tire used in industry to provide an inert atmos­
phere. A) К + 1/2H 2 KH
B) 2K + 0 2 —> K20 2
E) do not form com pounds with any other ele­
C) 6K + A120 3 2A1 + 3K20
ments.
D) К + H20 KOH + 1/2H 2 /
4. Consider these elements : E) К + CsCl -> KC1 + Cs
X : Is 2 2s 2 2p 6 3s 2 Зр 1 Y : Is 2 2s 2 2p 6 3s 2 3p 5
Z : Is 2 2s 2 2p 6 3 s 1 L : Is 2 2s 2 2p 6 3s2 3p 6
10. 0.2 mol of bromide of an alkali metal weighs
33 g. If the M has 48 neutrons, what is the period
I. Y is an halogen.
number of M ? (Br:80 g/mol atom)
IL X is a nonmetal.
A) 3 B) 4 C) 5 D) 6 E)^7 " .
ILL X is the alkali metal in the 3rd period.
IV. X and L do not form compounds. 11. X, Y, and Z represents the elem ents in IA
Which ones of these statements are true ? group.
 Some Selected Families In The Periodic Table 255

I. X has higher ionization energy than Y . 16. W hat is the family name of hydrogen ?
II. The atomic volume of Z is larger than that of X. A) alkali B) alkaline earth
III. Y has the strongest metallic character. C) halogen D) noble gas
Which one of the following rcpscrents the increas­ E) it is a family by itself
ing order o f atomic numbers of these elements?
17. Which one of the following is TRUE for the
A) X, Y, Z B )Z , Y ,X C) Y, Z, X
alkali metals as we go from top to bottom in the
D) X, Z, Y E) Z, X, Y
group?
A to m ic V a le n c e e le c tr o n I o n i z a t i o n m e t a llic
((12) A quantity of electricity that deposites 6 g of
ra d iu s num ber e n e rg y p ro p e r ty
Ca, also deposites 6.9 g o f an alkali metal from its
A) Increase Increase Increase Increase
molten iodide salt. W hich is the molecular weight in
B) Increase Unchanged Decrease Increase
g/mol of this alkali iodide ? 1=127, Ca=40
C) Decrease Decrease Decrease Decrease
A) 134 B) 150 C) 166 D) 232 E) 259
D) Increase Unchanged Increase Decrease
E) Unchanged Unchanged Decrease Increase
13. Which one is the atomic number of the nobel
gas in the fourth period of the peridoic table ? 18. 17 g of nitrate of an alkali metal gives 0.5 M,
A) 10 B) 18 C )3 6 D) 54 E) 87 400 mL solution. W hat is the atomic weight of the al­
kali metal ? (N=14, 0= 16)
14. X, Y, Z, and R represent the elements in the A) 3 B) 23 C) 39 D) 85 E) 133
same period. 19. X and Y represent the alkali metal and the ha­
I. X can only produce (1+) charged ions. logen in the same period. Which one of the following
II. Y is a monatomic gas at STP. is TRUE for these elements ?
III. Z has seven valence electrons. A ) X 1+and Y ^ a re isoelectronic.
IV. X and R combine to form the compound X 2R. B) Y has greater atomic number than X.
Which one of the following shows the increasing P ) The formula of their compound is XY 2.
order of atomic numbers of these elements ? ;T>J) The oxide of X is acidic and that of Y is basic.
A) X, R, Y, Z B) Y, Z, R, X С) X, Y, R, Z JE) The first ionization energy of X is greater than
D) X, R, Z, Y E) R, X, Z, Y that of Y.

20. X is the alkali metal in the fifth row of the

15. W hat would be the atomic num ber of the last periodic table. If 0.25 mol of the compound between X
element o f the seventh period if it were completed ? 80
and 35 Y is 41.5 g, which is the number o f neutrons in
A) 94 B) 96 C) 104 D) 118 E) 136 the nucleus of X ?
0 )4 9 B) 48 C) 47 D) 46 E) 45

\
 CHAPTER

Nuclear Chemistry

The objectives of this chapter are to enable the student to :

1. Explain the structure of nucleus.
2. Explain radioactive decay and discuss why it takes place.
3. Explain the different types of radioactive decay processes
and describe the characteristics of their radiation.
4. Write nuclear equations for radioactive decay processes.
5. Write equations for nuclear reactions produced artificially.
6. Explain the rate of radioactive decay and the half-life.
7. Calculate the energy equivalent of a given mass of matter
by using Einstein's equation .
8. Discuss nuclear fission as a source of energy.
9. Discuss nuclear fusion as a source of energy.
10. Discuss some of the practical, beneficial uses of radioiso-
to p e s .
 N uclear C hem istry 259

EX A M P LE 8.1 Understanding Radioactivity

Problem : Compounds XY, YZ arc radioactive but XZR is not. W hat comment can you say about the radio­
activity of a) X 2 b) Y 2 c) R 2 d) YR e) XZ
Solution : Radioactivity is a property of nucleus o f an atom. Therefore the radioactivity of an element is not
affected by its bccing free or in a compound. Since XZR is not radioactive, then, none of X, Z and R elements is
radioactive. XY and YZ arc radioactive because of the radioactivity of Y. So we can say that X 2, R 2, and XZ are
not radioactive but Y2 and YR are radioactivcs.

8.2.1 T Y P E S OF R A D IO A C T IV E D E C A Y
M any nuclei do n o t decay. T h ese are c alled sta b le n u clei o r sta b le
iso to p e s. The isotopes that break dow n spontaneously to new elem ents
are called the ra d io a ctiv e isotop es. T he stability o f a n u cleus m ay be e s­
tim ated by the follow ing rules.
1. A? the binding energy (energy needed to separate the nucleus into
individual protons and neutrons) p er particle increases the stability o f the
nucleus increases. Sec E xam ple 8.18.
2. Isotopes o f low atom ic numbers with a 1:1 neutron-proton ratio
are very stable. T he lighter stable nuclides have equal num bers o f neutrons
and p ro d o n s. In the n u c lid es w ith high ato m ic n u m b ers, b ec au se o f in ­
creasin g repulsive forces betw een protons, la rg e r n u m b e r o f neutrons m ust
be p resent to stabilize the nucleus and the neutron to proton ratio increases.
F o r b ism u th (Z = 83), the ratio is 15/1 .A ll elem en ts w ith ato m ic n u m b e rs
g re a te r th an 83, and som e lo w er, u n d e rg o the ra d io a c tiv e d ec a y . S e e
F ig u re 8.1.
FIGURE 8.1 S ta b l e n u c le i
3. Nuclei are particularly stable when they have either Z o r n equal to
are r e p r e s e n te d b y th e s h a d ­
e d area. T h e so lid line rep re­ 2, 8, 20, 28, 50, 82 or 126. T h ese nu m b ers h av e been called m a g ic n u m ­
s e n t s 1/1 n e u tr o n -p ro to n ra­ b ers. T h e nature o f these num bers have n o t been disco v ered yet.
tio. A m ong the naturally occurring radionuclides, only three kinds o f radi­
ations h ave been obscrv cd -alp h a, beta, and g am m a rad iatio n . See F ig u re
8.2 .

8 .2 .1 .1 ALPHA R A D IA T IO N

Я Ш A lp h a em issio n co nsists o f the e jec tio n o f p articles, w h ich h a v e an

7 atom ic n u m ber o f 2 and a m ass n um ber o f 4. a particles m ay be considered
to be p o sitively charged helium ion ( 2Hc2+). a particles have high ionizing
R a d io a ctiv e P 'J
+ effect, b u t low pen etratin g pow er. T h ey m ay be sto p p ed by a sheet o f p a ­
su b sta n c e

per. B ecause o f their positive charge they arc deflected by electric and m ag ­
netic field. T he sym bol for the a ray is jH c . The emission o f an a particle
by a nucleus reduces the atomic number by 2 and the atom ic mass number
FIGURE 8.2 T h e e ff e c t o f by 4. S ee F ig u re 8.3.
an electric field on ra y s from
a r a d io a c tiv e s u b s t a n c e .
E xam ples o f a decay are :
B e ta (p) ra y s a re e le c tro n s. 238
u , 234T h + ,H c ( a ) and
210
A lpha (a ) p a rticles are n u clei 92 90 111 84'Po 282Pb + ?He (a)
o f h eliu m a to m s. G a m m a (y)
rays a re sim ilar to X rays. N u c le ar eq uations and chem ical equ atio n s are n o t balan ced in the sam e
w ay. In n u clear reactions atom s change from one clem ent into an o th er one. A
258 Chapter 8

So far w e h av e discu ssed the ph y sical chan g es related to the state o f a

substance and ch em ical changes involving rearrangem ents and interactions o f
the v alen ce electro n s o f atom s o r m o lecu les. In this ch ap ter, w e are g o ing to
study the p ro cesses in v o lv in g changes in the nuclei o f atom s. T h e b ran ch o f
ch em istry th at d eals w ith th ese chan g es is called n u clea r ch em istry. N u c le ­
ar chem istry began w ith the discovery o f radioactivity and has beco m e im p o r­
tant during the p ast century.

8-1 THE STRUCTURE OF THE NUCLEUS

E v ery atom has a d ense co re called a nu cleu s. T h e nuclei o f all ato m s
co n sist o f sm aller particles. T h e m ain n u c lea r particles are the p roton and the
n eu tron , but th ere are m any o th e r particles. A t the presen t tim e n early 35 d if­
ferent subatom ic particles have been identified from the su bdivision o f atom s.
M an y o f these p articles arc unstable and e x ist for only a v ery sh o rt tim e. T he
status o f these p articles is not com pletely understood. S ec T able 8.1.

T A B L E 8.1 P ro p erties o f S u b a to m ic P articles

f
Particle Symbol Mass (amu) Mass (g) Electrical Charge
Proton 1.007276 1.672649x10 '24 1+
Neutron 1.008665 1.674954x1 O'24 0
Electron 0.0005486 9.109534xl0'28 1-
Positron 0.0005486 9.109534xl0'28 1+
Neutrino 0
Positive meson 0.150 2.50897x10 '25 1+
Negative meson 0.150 2.50897x1 O'25 . i-
2.42534x1 O'25
Neutral meson 0.145
0 __J
A positro n has the sam e m ass as an electro n b u t an opposite charge. P o ­
sitro n results from the c o n v ersio n o f a n u c le a r pro to n into a n eutron. W hen a
(3 particle o f less than m axim um energy is ejected, a n eu trin o, that carries o ff
the excess energy is em itted. T he particle, Jt m eson o r pion is a n u clear particle
th at h o ld s p ro to n s and n eu tro n s together. T h ree ty p es o f pio n s arc k n o w n to
e x i s t : p ositive, n egative, and neutral m esons.

8.2 RADIOACTIVITY
In 1895 R jtn tg en , a G erm an S cien tist, d isco v ere d X -ra y s th at p e n e ­
trate o p aq u e su b stan ces. In the fo llo w in g y ea r the F ren ch sc ie n tist H e n r y
T h e sp o n ta n e o u s c h a n g e
o f an u n s ta b le n u c le u s B ecq u erel fo u n d th at all uranium co m p o u n d s gave o ff p en etratin g rays. T he
into a n o th e r is c a lle d r a ­ intensity o f these rays w as proportional to the am ount o f uranium contained in
d io ac tiv e d ecay . T h e p ro ­
the com pound. B ecquerel called this pro d u ctio n o f radiation by uranium c o m ­
cess is c alled ra d io a c tiv i­
ty-
p o u n d s ra d io a ctiv ity . F o llo w in g B ecq u erel's d isco v ery , o th er e lem en ts that
T h e ra d io a c tiv ity o r ra d i­ radiate rays w ere identified by M arie C urie and her husband Pierre Curie.
o a c tiv e d eca y is s p o n ta ­ T h e n a tu re o f the rays w as ex p la in e d p rin cip a lly by E r n e st R u th e r ­
n e o u s b e c a u se w e h a v e
no c o n tro l o v e r it. ford . R a d io a c tiv e rays o rig in a te fr o m tra n sfo rm a tio n s th a t o c c u r w ith in the
n u c le i o f th e r a d io a c tiv e e le m e n ts.
 N uclear C hem istry 259

E X A M P L E 8.1 U n d e r s ta n d in g R a d io a c tiv ity

Problem : Compounds XY, YZ arc radioactive but XZR is not. What comment can you say about the radio­
activity of a) X 2 b) Y 2 c) R 2 d) YR c) XZ
Solution : Radioactivity is a property of nucleus of an atom. Therefore the radioactivity of an element is not
affected by its bccing free or in a compound. Since XZR is not radioactive, then, none of X, Z and R elements is
radioactive. XY and YZ arc radioactive because of the radioactivity of Y. So we can say that X2, R 2, and XZ are
not radioactive but Y2 and YR are radioactivcs.

8.2.1 T Y P E S OF R A D IO A C T IV E DECAY
M an y nuclei do n o t decay. T h e se are called sta b le n u clei o r stab le
iso to p e s. T h e iso to p es th a t b rea k d o w n sp o n ta n eo u sly to n ew elem en ts
a re c a lle d the ra d io a ctiv e isotop es. T he stability o f a nucleus m ay be e s­
tim ated by the follow ing rules.
1. A s the binding energy (energy n ee d ed to sep a ra te the n u cleus into
in d ivid u a l p ro to n s a n d neutrons) p e r p a rtic le increases the sta b ility o f the
nucleus increases. See E xam ple 8.18.
2. Iso to p e s o f low a to m ic num b ers w ith a 1:1 n e u tro n -p ro to n ra tio
are very stable. T he lighter stable nuclides have equal num bers o f neutrons
and p ro d o n s. In the n u c lid es w ith h ig h ato m ic n u m b ers, b e ca u se o f in ­
creasin g repulsive forces betw een protons, la rg e r n u m b er o f neutrons m ust
be present to stabilize the nucleus and the neutron to proton ratio increases.
F o r b ism u th (Z =83), the ratio is 15/1 .A ll elem en ts w ith ato m ic n u m b ers
g re a te r th an 83, and so m e lo w er, u n d e rg o the ra d io a c tiv e d ec a y . S e e
F ig u re 8.1.
FIGURE 8.1 S ta b l e n u c le i
3. N uclei are p a rticu la rly stable w hen they have either Z o r n equal to
are r e p r e s e n te d b y th e s h a d ­
e d area. T h e so lid line rep re ­ 2, 8, 20 , 28, 50, 82 o r 126. T h ese nu m b ers h av e been called m a g ic n u m ­
s e n t s 1/1 n e u tr o n -p ro to n ra­ b ers. T h e nature o f these num bers have n o t b een d iscovered yet.
tio. A m ong the naturally occurring radionuclides, only three kinds o f radi­
atio n s have been obscrv ed -alp h a, beta, and gam m a radiation. S ee F ig u re
8.2.

8.2.1.1 ALPHA RADIATION

A lp h a em ission consists o f the ejec tio n o f p a n ic le s, w h ich h av e an
atom ic n u m ber o f 2 and a m ass n u m ber o f 4. a p a n ic le s m ay be considered
to be p o sitiv ely charged helium ion ( 2Hc2+). a particles have high ionizing
effect, but low pen etratin g pow er. T hey m ay be sto p p ed by a sh eet o f p a­
per. B ecause o f their positive charge they arc deflected by electric and m ag ­
netic field. T he sym bol for the a ray is ^He. T he em ission o f an a p a rtic le
by a nucleu s reduces the a tom ic num ber by 2 a n d the a to m ic m ass num ber
FIGURE 8.2 T h e e f f e c t o f by 4. See F ig u re 8.3.
an electric field o n ra ys from
a r a d io a c tiv e s u b s t a n c e .
Exam ples o f a decay are :
B e ta (P) ra y s a re e le c tro n s.
A lp h a (a ) p a rtic le s a re n u c le i 292U 29> + 2Hc (a ) 3nd 284P0 282РЬ + 2He ^
o f h eliu m a to m s. G a m m a (y)
ra ys a re sim ilar to X rays.
N u c le a r eq uations and chem ical eq u atio n s are n o t balan ced in the sam e
w ay. In n u clear reactions atom s change from one clem ent into an o th e r one. A
260 Chapter 8

n u clear equation is balanced w hen tw o conditions are obtained.

1. T he su m o f the m ass num bers on each side is equal.
2. T he sum o f the a to m ic num bers on each side is equal.

£*•© •« .•A
i * r * e * »o *
A * 2e * * e
V o ° V o .V
Nucleus
*000
О Proton
* Neutron

FIGURE 8.3 E m issio n o f а п a p a rticle .^T h e e m is s io n o f a n a p a rtic le r e m o v e s 2

p ro to n s a n d 2 n e u tr o n s from th e n u c le u s, th e re fo re d e c r e a s e s th e a to m ic n u m b e r
b y 2 a n d th e a to m ic m a s s n u m b e r b y 4.

8 . 2 . 1 . 2 B E T A R A D IA T IO N
B eta ra d iation co n sists o f stream s o f e lectro n s, w h ich are called beta
p a rticles. T h e sym bol o f a b eta p article is because an electron has a m ass
n u m b e r o f 0 and a charge o f -1. A beta particle co m es from the n u cleu s o f an
atom . The beta p a rticle results fr o m the transform ation o f a neutron into a p r o ­
ton a n d an electron. See Figure 8.4.
B eta p articles have a greater penetrating p o w er but a low er ionizing p o w ­
e r than a particles. B eta particles are also deflected by electric and m agnetic-
T h e d a m a g e by ra d ia tio n
field.
is m o stly flue to the io n i­
z a tio n c a u s e d b y the fa st
m o v in g p a r tic le s c o llid ­
ing w ith m a tte r, a n d by
th e e x c ita tio n o f m a tte r ./ \
by у rays.
B io lo g ic a l tis su e m ay b e
e a s ily a ffe c te d by r a d ia ­ Helium -3
tHe
tio n . A flo w o f h ig h -
en erg y p a rtic le s m y cause
d e stru c tio n o f a v ita l e n ­
zy m e, h o rm o n e o r D N A FIGURE 8.4 E m issio n o f a b e ta pa rticle. T h e e m is s io n o f a b e ta p a rticle
n e e d e d fo r life o f a cell. re p la c e s a n eu tro n b y a proton, th e re fo re in c r e a s e s th e a to m ic n u m b e r o f th e e le ­
In g e n e ra l th e c e lls e x ­
m e n t b y o n e.
p o se d to ra d ia tio n d iv id e
m o re ra p id ly . T h e fa st- T h e n u clear equation for the form ation o f a beta particle is :
d iv id in g c e lls in c lu d e
c e lls in b o n e m a rro w , -> -°te + iP
w h ite c e lls, p la te le ts o f neutron beta particle proton
the b lo o d , and c e lls p r o ­ ( in n u c le u s ) (e m itte d ) ( le f t in th e n u c le u s )
du cin g im m une re sp o n se s.
T h e s e c e lls a re e a s ily The n et e ffec t o f /3 em ission is that the n u m b e r o f neu tro n s is d e crea sed
k ille d b y r a d ia tio n . T h e by 1 a n d the n u m b er o f p ro to n s is in c rea sed by 1. T h e m ass n u m b er does n o t
d e s tro y e d g e n e tik e ffe c ts change. E xam ples o f (3 decay are :
p a s s o n to s u b s e q u e n t 0 , 234n
g e n e ra tio n s . H -4 2He + °e , ^ M g -> t i A1 + -'Iе . " o T h ■29jP a + °,e ,and ->
 N uclear C hem istry 261

8.2.1.3 GAMMA RAYS

C h a n g e in C h a n g e in a to ­
E m iss io n G am m a radiation is e le c tro m a g n e tic rad iatio n o f v e ry sh o rt
a to m ic no m ic m ass no.
w avelength, у - radiation is caused by en ergy changes w ithin the n u cle­
a -2 -4
us. In n u c le a r equations, a p h o to n o f g am m a rad iatio n h a s the sy m b o l
P +1 0
oY o r o n ly y. B ecause gam m a rays have v ery h ig h en erg ies b u t n e ith e r
I 7
0
° J m ass n o r c h arg e, they h av e a g re at p en e tra tin g po w er. T h e refo re th e y
are n o t deflected by electric and m agnetic field. See F igure 8.2.
G am m a radiation frequently acco m p an ies all o th e r types o f radia-
tioactive decay. A n exam ple o f y - radiation is :
236
9?P u-> l& J J * + tHc [ 2atu]* 92 U + y

8.2.1.4 POSITRON EMISSION

Positron Emission, o r (3+ em ission, c o n sists o f th e e je c tio n o f a
p o sitiv e electron. T h e sym bol fo r the p o sitro n is °e. A p o sitro n has the
sam e m ass as an electron but a positive charge instead o f a negative charge.
I t a rises fr o m the co n versio n o f a p ro to n into a neutron. S ee F ig u re 9.5.
E xam ples o f positron em ission arc :
122. 122T 0
53 5 2 1e + I е l223Mg -> Na + fc

8.2.1.5 NEUTRON EMISSION

Neutron Emission is kind o f n u c le a r reaction th at form s an iso to p e o f
FIGURE 8.5 The e m is- parent nucleus. F o r exam ple, K rypton - 87 is a neutron em itter.
sion o f a positron replaces 87K r_ ^ 36*^
86Kr +
+ (Я
ln
a proton by a neutron. 36*^

8.2.1.6 ELECTRON CAPTURE (ec)

Electron capture is an o th er kind o f n u c le a r reactio n . In th is p ro c ess
the n u cleu s cap tu res an orbital e lectro n from the К o r L shell. T h e cap tu red
electro n ch an g es a n u clear p roton into a neutron. T h e n e t effect o f an electron
capture is th at the atom ic num ber is decrea sed by 1 a n d the m a ss num ber does
n ot change. E xam ples are :
197 197 106 106
Hg + ]C Au 47 Ag + °! 46
Pd
80 79

E X A M P LE 8.2 W riting and B alancing N uclear E quations

181
Problem : W rite the equations for the following examples of radioactive decay, (a) alpha emission by 78 Pt
(b) beta emission by 215]Na (c) positron emission by | 29Cu (d) electron capture by ” Ar
Solution :
(a) alpha emission by Pt An alpha emission reduces the mass number of the element by 4, then
181 it will b e : 181 - 4 = 177 or 181 = x + 4 => x = 177
Pt x\ + 4 He (a )
78 у 2 An alpha emission reduces the atomic num ber o f the elem ent by 2,
then it will be : 78 - 2 = 76 or 78 = у + 2 => у = 76
.... 181 177
Then the equation is : _ Pt 76
X + 2? He

(b) beta emission by 2^Na Mass number will remain the same but atomic num ber will increase
n Na - > * X + °j e (P) by 1. then x = 25 у = 12
Or 25 = x + 0 => x = 25 and 11 = у + (-1) => у = 12
The equation is : 25Na 25 V , 0 „
li 12 Л + -Iе
262 Chapter 8

(с) positron emission by 22 Cu Mass number will remain the same but atomic number will decrease
“ Cu —> *X + j с by 1. x = 62 у = 28 O r6 2 = x + 0 = > x = 6 2 ; 2 9 = y + l = > y = 28
The equation is : 2692Cu -> 2^ X + ®с

(d) electron capture by Jg Ar Mass number will remain the same but atomic number will decrease
,37 Ar + ^ e - > *X by 1. x =37, у =17 O r 37 + 0 = x => x = 37; 18 + ( - l ) = y = > y = 17
The equation is : 37 Ar + ® e —> ,377X

E X A M P L E 8 . 3 B a la n c in g N u clea r E qu ation s
Problem : How many alpha and beta particles arc radiated by 2 U to form 2<’67 Pb?
Solution : 238 U - > 20862 Pb + ?
The mass number is decreased by : 238 - 206 = 32. The decrease in mass number comes from alpha radiation.
Each alpha radiation reduces the mass number by 4. Then 32 / 4 = 8 alpha radiations were made. Each alpha radi­
ation decreases the atomic number by 2. Then 8 alpha radiations reduce the atomic number by : 2 x 8 = 16. But
in the equation the decrease in the atomic number is 92 - 82 = 10. The decrease would be 16 but it is 10. In that
case 16 - 10 = 6 beta particles must be emitted.
I238 U -> 20862 Pb + 8 4 He + 6 °, e 238 = 206 + 8 x 4 + 0 92 = 82 + 8 x 2 + 6 x (-1)

EXERCISE 8.1 One o f the naturally occurring decay scries is that of the nuclide 22y'||Th. The parti­
cles successively emitted in one route arc a , (3, {3, a , a , a , (3, a , (3, a . Determine the members o f the chain in
a sequence. 2H2 , >h

E X A M P L E 8 . 4 B a la n c in g N u clea r E qu ation s
Problem : 2 92u —> XX + He + 2 ^ e What is the mass and atomic number of the product X ?
Solution : Mass numbers and atomic numbers arc conserved in a nuclear reaction.
238 = x + 4 + 0 x = 234 1 234x
92 = у + 2 + 2 x (-1) у = 92 J 92

EXER C ISE 8.2 The uranium isotope 2 92U is a product of beta decay. It is itself radioactive and de­
cays by alpha emission. From what nuclide docs 2 93, U arise and what is the product of its decay ?
У! A a n dj 2 2pi)
2 33 v 9 t,

E X A M P L E 8.5 B ala n c in g N u clear E quations

Problem : XX 239Y+22He + 2®e What are the mass and atomic number of the initial radioactive element ?
Solution : From the conservation of atomic and mass numbers,
x = 239 + 2 x 4 + 0 = > x - 247 у - 93 + 2 x 2 + 2x (-1) = = > v - 95

EXERCISE 8.3 Balance the following equations.

a) 238X — > Y + 32Hc + 4 °, с b) 21 \X 237Y + ? + ? с) X -> 24’ Y + 2Hc + " c

E X A M P L E 8.6 C alcu lation s Based on N u clear R eactions

Problem : When 0.01 mol of 2937Np decays completely, 1.792 L He at STP is produced and 6 mol of beta
are emitted for each mole of 2937Np decayed. Write the balanced equation for this decay process.
Solution : If 0.01 mol 2937Np produced 1.792 L He during the decay, 1 mol 9337Np would produce 179.2 L
1of He. 179.2 L He at STP = 179.2 L/22.4 L/mol = 8 mol He
 N uclear C hem istry 263

W hen 1 mol of 2937Np decayed completely 8 mol of He and 6 mol of beta would be produced. Then, the equation
is: 2g,7 Np —> *X + ^ H e + 6 ®.e 237 = x + 8 x 4 + 0 => x - 205 1 205v
93 - у + 8 x 2 + 6 x (- 1) => у = 83 J 83

2 37Np —> 2g x + 8 ^He + 6 °,e

E X A M P L E 8 .7 C alcu latio n s Based on N uclear R eactions

ry.\
Problem : The Plutonium isotope, 94Pu, decays by beta emission. The product of this decay process is it­
self radioactive and decays by emission of an alpha particle. What arc the atomic and the mass numbers o f the
products of beta and alpha decays ?
Solution : The first decay can be written : 29]Pu —> 293X + °jC
Where the mass and atomic number of the product are found from the requirement that mass and charge arc con­
served. (That is, 241 =241 + 0 and 94 = 95 - 1 ) Applying the same conservation principles to the second decay
gives : 24*X 237Y + ^He

8.2 .2 NATUR A L AND A R T IF IC IA L R A D IO A C T IV IT Y

A ll elem en ts w ith atom ic num bers g re a te r th an 83 u n d erg o rad ioactive
decay. T h e decay o f one radioactive iso to p e leads to an o th er rad io activ e iso ­
tope. T h is iso to p e also decays to still an o th er rad ionuclide. T h e rep etitio n o f
th is p ro cess can co n tin u e th ro u g h a series o f n u c le a r reactio n s u n til a stable
isotope finally form s.
T h ree such disintegration series o ccu r in nature: th c 29^Th, 292U a n d 292U
400 2.0fS
scries. T h e 92U series, w hich lead s finally to the stable n u clid e, 82Pb is d ia­
g ram m ed in F igure 8 . 6 . T he 292U series co n sists o f 14 steps ; in v o lv in g 8 a ,
and 6(3 decays.

a P. У ft 7 а а, у a, у a

2gnTh J 215Pa ------------ ►

! ~U „ t >1 2|gTh ^-*1 2gRa — l .-»j ?||R n — l —► TlP°
[5X' 10 У 90_ 25 d 7 hr 2. 7 x 8 x l 0 4y l 2 хx 11037
0 3У | 86 4d
Uranium 10s У Thorium Polonium
a P /3,7
/3,7 a 0, 7
P, 0,7 v« - j .3 mi

82 Pb
n i 210p L _ l 210B| J 210pb L _ i 2»p0 L _ l--- liPb i
138 d " 5d 83 22y 82 ' - 1.6 X
x 84 20m i 83 27 mi
Lead Bismuth io~*« Polonium Bismuth
(a stable isotope)

FIGURE 8.6 The uranium-238 radioactive disintegration series.

In 1919, E rnest R utherford b o m barded nitro g en gas w ith a particles and

the first artificial transm utation o f one elem ent into another w as obtained.
14 17
o + \H

In 1934, Irene Jolio t-C u rie d iscovered th at w hen alu m in u m , b o ro n , and

m agnesium atom s w ere bom barded w ith a particles from polonium , the radio­
active isotopes could be artificially produced.
^ 30 p 1
> + 42Hc 15 0П
105B + 42He ■ , 37N + on
Radioactive
264 Chapter 8

R a d io n u c lid e s m ay be ; S ince that tim e, hundreds o f artificial radioactive nuclides have been p ro ­
u sed to le a m the d e ta ile d d u ced b y a v ariety o f n u c lea r reactions. N u cle ar reactio n s have b een used to
stru c tu re o f c h e m ic a l re- p rep are 0Ve r 1000 radionuclides in term s o f transm utations and m any are iso ­
topes that d o o ccu r in nature.
A larg e n u m b er o f uses have b een d ev elo p ed for th e iso to p es in re­
search, m edicine, and technology.

E X A M P L E 8.8 Completing and Balancing Nuclear Reactions

Problem: Find the mass and atomic number of the elements produced by the given artificial radioactive reac­
tions. a) 9 Be + 4He - > ? + ‘„n b) 284Si + 2 H —> ? + 50n
Solution :
a) 9 Be + 2He —> ? + !()n From the requirement of the conservation of the mass and atomic numbers,
9+4=x+l x = 12 1 j 2
4 + 2=x +0 x = 6 J 6

b) 284Si + 2 H — > ? + l0n 28 + 2 = x + 1 x = 29 1 29

14 + 1 = x + 0 x = 15 J 15x

EXA M P LE 8.9 Completing and Balancing Nuclear Reactions

Problem : Find the particles which are emitted by the given artificial radioactive reactions,
a) 57N + lQn — > ^B + ? b) 9 Be + 2H —» ,05B + ?
Solution :
a) 7N + Qn — > 5В + ? 14 + 1 = 11 + x x =4 1 4
7 +0= 5 +x x = 2 J 2 =2
b) 94Be + 2H — > 105B + ? 9 + 2 = 10 + x x=l 1 l x _ ln
4 +1 = 5 + x x = 0 J 0 <)П

EXERCISE 8.4 Find the mass and the atomic number of the product and the particles which arc produced
a) 23Al +
by the given reactions. + 2Hc b) f 3AI + 2H c -> ^P +... a) f j xb) ' 0n

E X A M P L E 8 .10 Understanding Artificial Radioactivity

Problem : When element X is bombarded with a particles it produces another element Y and a neutron. If Y
has 6 neutrons and is in the 2nd period and IVA group, find the atomic number and atomic mass number of X?
Solution : Since Y is in the 2nd period and IVA group its electron configuration is: Y: Is 2 2s 2 2p 2
So Y has 6 protons. Its atomic mass number is: A = p + n = > A = 6 + 6 = 12.
The nuclear reaction described in the problem may be written as follows: X + 2He —>^ Y + ^n
From the conservation of nucleons in nuclear reactions we find that X has the atomic number 4 and atomic mass
number 9.

EXER C ISE 8.5 When element X captured a neutron, it produces another clement Y and an a particlc.lf Y
is in the IA group of the 3rd period and has 13 neutrons find the atomic and atomic mass numbers of X? 13-27

8.3 RATE OF RADIOACTIVE DECAY

T h e rates o f d ecay can be m easured by G eig c r-M Q lle r co u n ter, W ilson
cloud c h am b er and o th e r devices. D ifferen t radioactive elem ents d ecay at d if­
ferent rates. T h e rates o f decay o f all radioactive su bstances is in d ep en d en t o f
tem p eratu re. T h e rate o f d ecay d ep ends o n ly upon the am o u n t o f rad io activ e
 N uclear Chem istry 265

substance p resent initally. T he rates o f decay o f radioactive substances m ay be

exp ressed in term s o f half-life.
The h a lf-life o f an iso to p e is the tim e req u ired f o r h a lf o f the sa m p le to
d eca y a n d d e n o ted by t j ,2
As sh o w n in F ig u re 8.7, the cu rv e in d ic ates the re la tio n sh ip b e tw e en
n um b er o f radioactive atom s and time.
........ .....
Number of Time Number of Percentage ^
half-lifes Passed atoms left decay
0 0 N0 0
1 t l /2 N(/2 50 %
2 2 t l /2 N ^4 75 %
3 ЗЦ /2 N </8 87.5 %
n nt l /2 N(>/2n (100-100/2") % ,
V

FIGURE 8.7 R a d i o a c - T h e re fo re w e can o b tain an ex p ressio n related to the in itial and Final
tiv e d is in te g r a tio n a n d m asses o f the radioactive substance.
ha lf life. In e v e r y h a lf life, ,
th e n u m b e r o f a to m s (or m= ^ 1 m 0 -> initial mass n = -L ) t -4 time passed
mass) r e m a in in g is 2 " J m —> mass left U /2 J h /2 —» half-life

halved' H a lf-life is a c h a rac teristic p ro p erty for each rad io activ e elem en t. S ec
T able 8.2 for the half-lives o f som e com m on radioactive elem ents.
T A B L E 8 .2 T h e h a lf- liv e s o f s e v e r a l r a d io n u c lid e s
r Radiations or N
Element Isotope Half-Life Mode of Decay
Naturally Occurring Radionuclides
Potassium 40ъ- 1.3xl0 9 years beta, gamma
19
Tellurium 123 To 1.2 x l 013 years electron capture
52lc
Neodymium ’fioNd 5 x l0 15 years alpha
Samarium «Sm 4xlO H years alpha
Rhenium 222r p 7 x l0 10 years beta
86
Radon 222pn 3.82 days alpha
86
2 2 6 p ,,
Radium 88 1590 years alpha, gamma
Thorium 2lgTh 80.000 years alpha, gamma
Uranium 2i l u 4.51xl09 years alpha
Synthetic Radionuclides
Pydrogen (tritium) 12.26 years beta
Oxygen !i o 124 seconds positron
32p
Phosphorus 15K 14.3 days beta
Technetium 43TC 6.02 hours gamma
Iodine ! 53l 8.07 days beta
Cesium ЧбСз 30 years beta
Strontium 38S r 28.1 years beta j
266 Chapter 8

E X A M P L E 8.11 Calculations related to Radioactive Decay ^

Problem ;T h e half-life o f № is 1 hour. W hat mass of 64 g o f sample will remain undecaycd after 4
hours?
Solution : m 0 = 64 g 'j the number of half-lives in 4 h is:
m=? I n= = 4h/l h = 4
t=4 h J So the mass of the radioactive element will be halved 4 times.
И/2 = 1 h
64 32 16 8 4 g
1h 1h 1h 1h
4 g of Bi will remain undecaycd at the end of 4 h. Or wc may solve the problem by using the formula: m=m(>/2n
m = 64/24 = 64/16 = 4 и

E X E R C IS E 8.6 The isotope P/Co has a half-life o f 5.27 years. What amount o f a 1 g sample of 17 C0
remains after 15.81 years ? 0.125 g

E X A M PLE 8.12 C a lc u la tio n s R e la te d to the R a d io a c tiv e D ecay

Problem : 75 % of a radioactive element decays in 20 hours. What is its half-life ?
Solutio n : m o = 100 _m0 ” m „ _ 100
m = 100 - 75 = 25 m 2 ~ ~ - — - 4= >n-2
t = 20 hours ^
n=— 2=M => 11/2= 10 h
1 1/2 tic

E X A M P L E 8 .1 3 Calculations Related to the Radioactive Decay

Problem : What percent of a radioactive element decays in 5070 years if its half-life is 1690 years ?
Solution :
n = -L = ^ Z 0 = 3 m = — => =1®2. = ж = 12.5% remains and 100 - 12.5 = 87.5 % decays
tic 1690 2» 23 8

Second way : n = =3
1690
m . m
too ----------------- 50 25 12.5 100-12.5 =87.5% decay
1690 year 1690 year 1690 year

E X E R C ISE 8.7 The half-life of ']fA g is 3.20 hours. How long will it take for 75% of a sample to disap­
pear ? 6.40 h

E X A M P L E 8 .1 4 Calculations Related to the Radioactive Decay

Problem : 24Na decays according to the following equation, n N a —> 24Mg + 0}е Half-life of 24Na is 15
hours. a) How long does it take to decay 87.5% o f j24Na ? b) W hat percent of Na decays in 75 hours ?
Solution: The initial mass of the substance will be accepted as 100 %.
a) m 0 = 100%
 N uclear C hem istry 267

b) n = J - = ? i = 5 times halved m = — => m = 1 ^ = 3.125 remain 100 - 3.125 = 96.875 % decay

t* 15 2" 2

100 50 25 12.5 6.25 3.125

1 2 3 4 5

E X A M P L E 8 . 1 5 C alculations Related to the Radioactive Decay

Problem : Suppose the elements of the earth were created 5 x 109 years ago. W hat fraction o f a nuclide with
a half-life of 1 x 108 years would still remain today ? t 5 10? 1
Solution: t = 5 x 109 years n = — = — — ^ = 5 x 1 0 = 5 0 times halved
11/2 = 1 x 108 years № 1 x 10
mn т 1 so -16
m=— — = —-r = (1/2) = 8 .8 8 x 10
v mr 2

EXERCISE 8.8 The half-life of a nuclide is IxlO 9 years. In 4 x l ()9 years, its 3 grams decayed. W hat was
the initial mass o f the nuclide ? s

E XA M PLE 8.16 C a lc u la tio n s R e la te d to th e R a d io a c tiv e D eca y

Problem : An clement has two radioactive isotopes A and B. The half-life of A is 5 times that of B. A sam­
ple is prepared containing both isotopes. In a period of time t, the concentration of A falls to half its initial val­
ue. W hat fraction of the initial concentration of В remains ?
Solution : The concentration of A falls to half its initial value. In that case n of A is 1.
n = — =1 t = 11/2 Half-life of Ais equal to t
l l/2
t t с mo m„ mQ
Then the half-life of В is t/5 n = r - = U7 = 5 m =_7= fractlon of B rcmains
11/2 V j 2 2

E X A M P L E 8 .17 C a lc u la tio n s R e la te d to th e R a d io a c tiv e D ec a y

Problem : When the radioactive element A decays to give B, one alpha is emitted. The half-life of A is 64
days and the AW of A is 210. To obtain 1.68 liters of He al 0°C and 2 atm pressure in 192 days, what must be
the initial mass of A ?
S o lu tio n : _ P x V _ 2 atm x 1.68 L
2Юд 206B + 2h c пн» R xT 22.4/273 L atm/mol К x 273 К

To em it 0.15 mol of He, 0.15 mol of A must decay. It is 0.15 x 210 = 31.5 g. rn = the remaining part of A. If
the initial mass is m 0 , m = m 0 - 31.5

n =— =1 ^ = 3 m =— m 0- 3 1 . 5 = m 0/8 8 m 0- 252 = m o m „=36g

tie 64 2"

EXERCISE 8.9 How long docs it take to decay 3/4 of a radioactive element if its half-life is 3 years ?
6 \ears

8.4 NUCLEAR REACTIONS

N uclear reactions arc greatly used for both producing n u clear energy (nu-
cle a r w eapons, n u c le a r p o w e r plants, etc...) and prep arin g iso to p es b e lo n g in g
to elem ents that d o not exist in nature.
N u c le a r reactio n s to pro d u ce n u c le a r e n erg y arc fission and fusion re­
actions.
In a fissio n reactio n a h eav y n u cle u s is sp lit into nu clei o f lig h te r e le ­
m en ts and se v e ral neu tro n s. F issio n is the so u rce o f th e e n e rg y o f n u cle ar
p o w er plants, and the atom ic bom b. W hen a n eutron is absorbed by a uranium
235 235
iso to p e, 92U , th e 92U n u cleus splits into fragm ents and releases en erg y and
m o re n eutrons.
2925U + \)П - > 36 Kr + * ^B a + 3 '0n + energy
T h e n e u tro n s g iv en m ay sp lit o th e r uranium atom s and c o n tin u ally re ­
lease m o re n eu trons. T h is process is k n o w n as a chain reaction. S ee F igure

FIGURE 8.8 A c h a in re a c tio n . T h e fissio n o f a sin g le n u c le u s p r o d u c e s

s e v e r a l n e u tr o n s th a t c a u s e th e fissio n o f m o re nuclei.

A fissio n reaction m ay be used for both peaceful p u rp o ses and m ilitary

pu rposes. In atom ic bom b, the chain reactio n is allow ed to cascade, so that a
large n u m b er o f nuclei undergo fission alm ost sim ultaneously, releasing en o r­
m o u sly larg e am o u n ts o f en erg y . In a n u c le a r reactor, the ch ain rea ctio n is
c o n tro lled by in tro d u cin g n eu tro n -ab so rb in g rods m ad e -fro m b o ro n o r g ra ­
phite. So the energy is released slow ly o v e r a long period o f tim e.
Nuclear fusion is a p ro cess in w h ich v ery lig h t nuclei are fused into a
h e a v ie r n u cleu s. T h is pro cess lib erates m o re e n erg y th an fission pro cesses.
T h e h y d ro g en b o m b is based on n u clea r fusion. T h e e n erg y o f the sun is b e ­
liev ed to be d eriv ed from the n u clear fusion reaction. T h e nuclei o f hy d ro g en
atom s m ay be converted into helium by n u clear fusion.
 N uclear C hem istry 269

T he estim ated reactions on the sun are :

Jh + }h 2H + ®e
Те (j H -= D euterium )
2H + }h - » ^He + у
jHe + ^He —> 2Hc + 2} И

8.4.1 TH E E N E R G Y IN V O L V E D IN N U C L E A R
REACTIONS
N u clear reactions, sim ilar to ch em ical reactions, can be e ith er cn d o th cr-
m ic o r exotherm ic. H ow ever the quantity o f energy in a nuclear reaction is a p ­
p ro xim a tely a m illion tim es greater than the energy in chem ical reactions. T his
is b e c a u se o f the larg e ch ange in m ass in a n u c le a r reactio n . T h e e n erg y re ­
leased in a nuclear reaction is readily calculated from the difference in m ass b e­
tw een the reactan ts (the parent nucleus) and p ro d u cts (the daughter nucle­
us). E nergy and m ass arc related to each o ther by E instein's equation,
E = m e2
w here E = energy, m = ch an g e in m ass, с = speed o f light. C o n sid er
the follow ing reaction : 3H + 2H —> 2Hc + ]()n
T h e change in m ass, Am, (som etim es so called m ass defect) is:
iH 2H e <P
3.01605 2.01410 4 .0 0 2 6 0 1.00867

5.03015 5.01127
Am = 5.03015 - 5 .0 1127 = 0.01888 g
T he energy equivalent o f this difference in m ass m ay be calculated as fol-
low s.
E = m e2
= (1.888 x 10 '5 kg) x (3.00 x 10 8 m /s )2
= 1.70 x 10 12 jo u le s = 4 .0 6 x 10 11 calories = 4.06 x 10 8 kcal/m ol

EX A M P LE 8.18 C alculating the Energy in a Nuclear Reaction

Problem : W hat is the energy associated with the a decay of 238U (a) in kJ/mol (b) in kcal/mol ?
238. т ч 234™ , 4Ыл
92 — 90 2
The nuclidic masses in amu (= g/mol), are 292U = 238.0508, 2<H)Th = 234.0437, ~ 4.0026
Solution : The change in mass = 238.0508 - (234.0437 + 4.0026)
= 0.045 g/mol = 4.5 x 10'6 kg/mol
E = me 2
E = (4.5 x 10'6 kg/mol) x (3.00 x 108 m/s )2 = 4.05 x 10 11 joulcs/mol
= 4.05 x lO’ VlOOO = 108 kJ/mol = 4.05 x 108 kJ/mol/4.184 = 9.68 x 107 kcal/mol.

E X A M P L E 8 .19 Calcu latin g the E nergy in a Nuclear Reaction

Problem : W hat is the energy associated with the following hypothetical nuclear reaction ?
2 |Н + 2дП — > 2Hc
Solution : Masses o f the reactants : Mass of p ro d u ct:
2 protons = 2 x 1.00728 amu = 2.01456 amu Mass of 1 mol of 42He (observed) = 4.00260 amu.
2 neutrons = 2 x 1.00867 amu = 2.01734 amu Am = 4.03190 - 4.00260 = 0.0293 amu or g/mol.
Total mass of reactants = 4.03190 amu
270 Chapter 8

E = m e2
= (2.93 x 10"5 kg/mol) x (3 x 108 m/s )2 => 2.64 x 1()12 J/mol =>' 2.64 x 109 kJ/mol => 6.32 x 108 kcal/mol

E X A M P L E 8.20 C a lc u la tin g th e B in d in g E n e r g y in th e N u c le u s o f an A to m
Problem : The nucleus of an ordinary helium atom contains two neutrons and two protons. Its mass, and
those of a neutron and a proton arc respectively 6.64462 x 10"27 kg, 1.67495 x 10‘27 kg and 1.67265 x 10 27 kg.
Calculate the binding energy for 4He.
Solution: : The difference between the sum of the masses of the nucleons constituting the helium nucleus and
the masses of the nucleus itself is :
A m = (2 x 1.67495 + 2 x 1.67265 - 6.64462) x lO '27 kg => Am = 5.058 x 10'29 kg
Hence by the Einstein relation the difference in mass corresponds to an energy o f :
E = A m .c 2 = (5.058 x 10 29 kg) x (3.0 x 108 m/s )2 => 4.5522 x 1042 joule
This is a huge energy for the formation of just one nucleus. For 1 mol of He nuclei the binding energy is :
E = 4.5522 x 10 42 joule x 6.02 x 1023 = 2.74 x 10 12 joule => 6.555 x 10 11 calories =6.55 x 10 8kcal

E X A M P L E 8.21 C a lc u la tin g th e E n er g y R e la te d to th e N u c le a r F u sio n

Problem : a) Calculate the energy released by the fusion : jH +j’H —>jH c
b) W hat percent of the total mass of the starting materials is converted into energy ?
The atomic masses are : }h = 1.0078 amu 2H = 2.0141 amu ^He = 3.0160 amu
Solution : M asses of the reactants: (1.0078amu) + (2.0141 amu) = 3.0219 amu
mass of the p ro d u c t: (3.0160amu)
Am = 3.0219 - 3.0160 = 0.0059 amu = 0.0059 g/mol
E = m e 2 = (0.0059 g) x (3 x l ()10 cm/s )2 = 0.0531xl020 erg = 0.0531 xlO 13 J = 0.0127xl013 cal =* 1.27xl0u cal
b) Starting materials = 3.0219 amu mass difference 0.0059 amu
0 0059
then, —— -— x 100 = 0.195 % of the starting materials is converted into energy.
3.0219

E X A M P L E 8.22 C a lc u la tin g th e M a ss R e la te d to th e N u clear E n erg y

Problem : How many kg of carbon must be burned to obtain the energy which is produced by changing 0.2 g
mass into energy ? M olar heat of combustion of С is 94.0 kcal.
Solution : The energy of equivalent of 0.2 g is :
E = me 2 = 0.2 g (3 x Ю 10 cm/s )2 = 1.8 x 1020 erg = 1.8 x 10 13 joule

= L 8j M 0 _ jo u le = 0 43 x 1 0 13caj = 0.43 x 10 “ kcal

4.18
When 1 mol (12 g) carbon is burned, 94.0 kcal is produced
__________ x g o f c a r b o n ___________________ 0.43 x 10 10 kcal
10
0 .4 3 x 1 0 x l 2 g c , 1A8 - c 1A5, CCA, ,, , ,
x = ----------------------- sl = 5 .5 x 1 0 g = 5.5 x 10 kg = 550 tons must be burned.

EXER C ISE 8.10 Calculate the energy rclascd by the fission : + '()n — > 94xSr + ' 54X0 + 3 '(|n
The atomic masses arc: "i^ ll = 235.044 amu, '^ S r = 93.915 amu, *54X0 = 138.918 amu, and
the mass of neutron = 1.0087 amu. 1 . 7 42 4 x ! 0 U J

EXER C ISE 8.11 The nucleus of an ordinary lithium atom contains four neutrons and three protons. Its
mass and those of a neutron and a proton arc respectively 11.65063 x 10’27 kg, 1.67495 x 10'27 kg and 1.67265
x 10' 27 kg. Calculate the binding energy for 1 mol of 7I.i nucleus. 3.636 x 1()'2 J
 N uclear C hem istry 271

SOM E NEW TERMS

Alpha em ission is a stream o f alpha particles atoms present in a sample to undergo radioactive de­
produced by radioactive decay. cay.
Alpha particle is the nucleus of a helium atom. N eutron em ission is a nuclear reaction in
Beta em ission is a stream of electrons produced which a neutron is ejected.
by radioactive decay. Nuclear fission is a radioactive decay process in
Beta particle is an electron emitted in a radioac­ which a heavy nucleus breaks up into two lighter nu­
tive decay. clei and several neutrons.
Electron capture is a form o f radioactive decay Nuclear fusion is the formation o f atom ic nu­
in which an electron from an inner electronic shell ab­ clei by the fusing together of the nuclei o f lighter iso­
sorbed by a nucleus. topes.
Gamma radiation is a stream of very high ener­ Positron is a positive electron emitted as a result
gy photons emitted from atomic nuclei. of the conversion of a proton to a neutron in a radioac­
Half-life is the time required for one half of the tive nucleus.

R E V IE W Q U E S T IO N S
9.1 Why do stable nuclei never have more protons a) temperature b) pressure c) physical state
than neutrons ? d) being free or in a compound
9.2 W hat three kinds of radiation have been ob­ e) being a neutral atom or ion
served from naturally occurring radionuclides ? How do I) quantity of element g) being pure or impure
you distinguish these particles? 9.8 As the atomic number increases, the ratio of
9.3 W hat is the meaning o f each of the following neutrons to protons increases. W hat does this suggest
symbols? a) a b) P с) у d) tj /2 e) P+ f) P' as a factor in nuclear stability ?
9.4 W hat is the difference between P+ decay and 9.9 Radionuclides of high atomic num ber arc for
electron capture if both decrease the atomic number by more likely to be alpha emitters than those of low
one? atomic number. Offer an explanation for this.
9.5 Why is the penetrating ability of alpha radia­ 9.10 W hat are the differences and similarities be­
tion less than that of beta or gamma radiation ? tween nuclear fission and nuclear fusion ? Where does
9.6 If electrons do not exist in an atomic nucleus, the evolved energy come from in each case ?
how can an electron in beta radiation com e from the 9.11 A fission reaction is started by a neutron en­
nucleus ? tering the nucleus of a uranium atom. W hy is it much
9.7 Indicate the effect of each of the following on easier for a neutron to enter an atomic nucleus than it
the half-life of a radioactive clement. would be for a proton to enter a nucleus ?

R E V IE W P R O B L E M S
R ad io a c tiv e P ro c e ss e s
222
9.3f2 Com pounds X 2Y, XZ 2, XR, X 3T arc radio- a) 86Rn decays by a emission
active'but YZ and R Z 2 arc not. W hat comment can b) 292U decays by P' emission.
238
you give about the radioactivity of each of the ele­ c) 92U decays through two successive a emissions
ments ? X is r a d i o a c t i v e and one P" emission.

9.13 W hat are the atomic and atomic mass num ­ d j ^ B i decays through two successive a and two
bers of the nucleus obtained in each of the following successive P" emissions.
processes? e) 33AS decays by P+ emission.
 272 Chapter 8

9.14 Supply the missing information in each of c) A proton combines with 12C to form a particle
these natural decay processes. Z and a photon.
a) ,X -> 8°Y + 2 a + 2p
9.17 An element becomes a member of IIA group
after 2 alpha emissions. W hat was the group number
c)29oTh -> 288°2fx + 6? + 4p"
235, 207 of the element before radiation ? via
d) 92/ 82
Y + ?? + ??
e) 292U -> jX + 7a + 4p 9.18 1 mol 232U produces 156.8 L helium at
STP and it radiates 4 p at the same time. W hat is the
9.15 Complete the following equations. 207
mass and atomic number of the product ? 82 P b
a) 2з7А1 + 2H ?+a
b) ^Be + a -> ’62C + ? 9.19 2 Be + 2H —> X + дп
c) ? + 2H 4B e + у W hat is the group and period number of X ?
238 14x 246,
X
d) 92 U + 7 N — > 7 + ?д П 2 n d P, IA
ч 2 3 8 , T , r, „ 247c , C1
e) 92U + ? —> 99HS + 50n 9.20 One of the naturally occurring radioactive de-
235
cay series begins with 92U and ends with the forma-
9.16 Give the chemical symbols, atomic numbers 207
tion of stable 82p b- How many a and how many p
and mass numbers of X, Y, and Z in the following
emission are involved in this series ? 7a, 4 p
nuclear reactions.
a) A neutron reacts with 6Li to form an a particle
^,21 Why is it impossible for the following reac­
plus a particle, X.
tion to take place?
b) An a particle combines with 14N to yield a pro­
}H + jH -> ^ H e
ton and a particle, Y.

H a l f - L if e
9.22 A radioactive element, X has a half-life of 9.27 How long will it take for 15/16 of a radioac­
5 s. If you had 32 g sample of X. How much X would tive sample to decay, if its half life is 2 days? 8 days
you have after
a) 5 s. b) 10 s. c) 20 s. d) 12 s. 9.28 The half-life of a radioactive elem ent is 8
years. There is a 40 g difference between the masses of
9.23 T he nuclei '799 Au has a half-life o f 64.8 rem aining substances betw een 16lh and 24lh years.
hours. How much of 0.0100 g sample remains at the How many grams of the substance will remain behind
end o f 13.5 days ? 3.l25xl0'4 g after 32 years ? 20 g

/?к2Ф А radioactive nucleus has a half-life o f 30 9.29 The 14C activity in a piece o f wood is about
m m rw h a t percentage o f a sample will remain undc- 0.250 limes that existing in comparable living matter
caycd after 1.5 h? 1 2. 5 % today. W hat is the approximate age of the wood ? The
half-life of 14C is 5730 years. 1 14 6 0 yr.
9.2f^bisintegration of 93.75 % o f a radioactive
element takes 160 years. W hat is its half-life ? 9.30 The radioactive decay of TI-206 to Pb-206
has a half-life of 4 min. Starling with 8 x l0 22 atoms of
40 years
9.26 Calculate the time required for 87.5 % of TI-206, calculate the numbers of atom s left after 20
222 . 21
Ra to decay. The half-life of Ra-222 is 1590 years. mm. 2.5x10
4770 yr
 Nuclear Chemistry 273

253 2z.3 0
The graph show s the rate 9.33 у y Es and ^ ’U both radiate a particles
9.31
when decayed. If 1 g of pure Es and 1 g of pure U arc
of disintegration of a radioac­
placed into a 1 I. evacuated container at 0°C, what will
tive elem ent a) W hat is the
be the pressure in the container after 20 days? Half
half-life of the elem ent? b)
lives of both are 20 days. 9 . 3 x 1 O'2 at m
What is the mass of the cle­
ment decayed between 411' and
5th hours? 9.34 The radioactive |4yK decays to Ar with a
>9
half life of 1,2 x 10 yr.
ЧХ •
9.32 Half-life 17C'I is 40 minutes, and it radiates a) Write a balanced equation for the nuclear change.
38, b) A sample of moon rock is found to contain 25%
P particles. If 4 moles of H j7CI arc placed into 62.4
L container, the pressure is m easured to be 1650 К-40 and 75% Ar-40. Calculate the age of this moon
mmHg alter 80 minutes. What is the temperature in rock in years.
the container ? -100 К 2.4x10 yr

N u c le a r R ea c tio ns
9.35 Given 2 JH +- 2,'n -> 4lle 9.38 The energy released by the decay o f j\JS by
When I mol o f He is formed, 0.03 g of mass positron emission is 5.40 MeV. The nuclide produced
31
changes into energy. What is the binding energy of 1 j 5 V has a mass ol 30.97376 amu anil the mass ol po­
mole of He ? sitron is 0.0005486 amu. What is the mass of j^S ?
I eV - 23.06 kcal I amu = 931 mcV)
9.36 The formation o f 2 moles o f liquid water 3 0 . 9 SO 0 9
from gaseous oxygen at 25°C and 1 atm is accom pa­ 9.39 Identify the fission and fusion reactions in
nied by the release of 572 kilojoulc. What is the loss the following processes.
in weight (in gram) during this reaction ? What is the
percentage loss in weight ? I t- jll —> 2He + у
a) [H
6.36x10 ;1.77xl0'H p e r c e n t I 4 235, , 1 111., 92,, ,1
b) у >IJ + 0n 56Ba + 36k r + 30n
9.37 The nuclide 'y iP l decays to ‘^ O s by alpha
emission. The mass of '/ « f t is 191.9414 amu, the 9.40 The bom bardm ent o f F-19 by a particles
produces Na-23 and neutrons. Write the nuclear equa­
mass of *7*Os is 187.9560 amu and the mass of ^He
tion for the transmutation.
is 4.Ш 260 amu. Calculate the energy released in this
process.
2.52x1 o " Jim о I
274 Chapter 8

SELF TEST
1. Which nf the following nuclei would you e x ­ radioactive emissions. Which is this emission ?
cept to he unstable ? A) 2 a , 2\] B) 2 a . у С) 2|L у D) a , p E) 2 a , P
А )|Н B ) ' 71N C ) j > D) '47Ag E) l i j R a
9. W hich o n e o f the follo w in g s ta te m en ts is
2 . If a radioactive elem ent emits beta particles, W RONG ?
which one o f the following is true ? A) If an atom emits one p particle, one of its n e u ­
A) Number 0Г neutrons decreases by 1 trons is transformed into one proton and one electron.
B) Number of protons decreases by 1 B) If an atom captures one electron its atomic num ­
•C) Atomic number decreases by I ber decreases by one.
D) Mass numlrer decreases by 1 C) If an atom em its a positron its num ber o f p ro ­
E) Number of electrons decreases by I . tons increases by one.
D) 11 an atom emits one a particle its proton n u m ­
3. I: XY is radioactive bers and neutron number decrease by 2 each.
11: X ZT is radioactive E) If an atom emits one a and two p “ particles the
111: XT is not radioactive isotope of the same element is formed.
Which one of the following isn't radioactive?
A) X2 B) YT C ) Z 2X D) Y2 E )X Y T 10. As a sample o f radioactive nuclide decays, its
half-lilc
4. Which one of the following does not represents A) decreases 13) remains the same C) increases
a nuclear change ? D) sometimes increases, sometimes decreases
A) + 2(,n - ? jllc E) any of the above, depending u|K>n the isotope
13
N + ,ln
p , 235 .. , 1 92., 141,. -.1 11. The first nuclear reaction ever observed o c ­
C i . 9 , 2 . y + ,w 4 36K r + 5 n B a + 3 <)n
curred w hen 17N was bom barded with alpha particles
D) H2 -> H + H
and protons were ejected. This reaction produces :
E ) jftFc -> 25 N! ” + P+ A ) ' 77N B) '([o o \;F D) IoNe Ej'x'O

5. Which types of radiation arc affected by electric "^78 226

12. When i) 2 LI changes into ()1 Pa, how many
and magnetic field ? alpha and beta particles arc emitted ?
A) only a B) only p C) only у A) 3 alpha B) 3 alpha C) 5 alpha
D) a and p E) a , p, and у 4 beta 5 beta 3 beta
D) 3 alpha E) 4 alpha
6 . X + ot -> Y + Jh 6 beta 4 beta
Y + ,',11 - > Z + у
If element Z is in the Зк1Р and IVA group, w hifh 13. Which particle m ust be absorbed by 7cFe to
5T
is the atomic num ber o f X ? produce Y;Mn ?
A) 11 B) 12 C )13 D) 14 E) 15 A) electron B) positron С ) neutron
Df alpha E/f gam m a
7. If an elem ent is exposed to a neutron field, it /
captures a neutron, and disintegrates by emitting 2 a 14. If an element- in the IA group em its 1 alpha 2
т I9
particles, forming ‘ 87X. Which one ol the following beta particles w hat will be the group num ber of the
is the original element ? new element ?
A4 22 7 A r.4 2 2 6 A 227 A r v . 22 5 A Г ч 22 6 A
A) IA B) IIA C) IIIA D) IVA E) VIIIA
A ) 91A B) 9 j A C) 90 A D) 92 A E)

“>38 °3() 15. How long does it take to decay 63 g o f a radi-

<4. у becomes 4()Y alter a series ol successive
 Nuclear Chemistry 275

outlive element which is 64 g inilially and has a ha 11- many neutrons does the final isotope possess ?
life o f 32 years ? A) 134 B) 137 0 140 D) 141 E) 153
• A) 48 B) 96 C) 102 D )1 5 2 H) 192
1 9 . After 100 years 12.5 gram s o f a radioactive
16. After two hours, 1/16 of the initial amount ol element, which was 200 g initially, remains behind.
a certain radioactive isotope remains undbeayed. Which Which is its half-life in years?
is the half-life of the isotope? A) 10 11)20 0 25 D) 33.3 E) 50
A) 15 min B) 30 min C) 45 min
D) 60 min E) 90 min 2 0 . W hen a radioactive elem ent em its one alpha
and two beta particles, which one of the following will
17.1 lie decay o f 93.75 % of a radioactive isotopebe W RONG ?
takes 32 minutes. W hich is the half-lile o l-th e iso- A) atomic number remains the same.
tO|K:? B) mass number decreases by 4.
A) 2 min B) 4 min C) 6 min 0 ) 8 min E) 16 min ( ') its another isotope is formed.
I)) its place in the Periodic fable doesn't change.
18. A radioactive isotope having 146 neutrons E) the number of nucleons remains ilia same.
disintegrates by emitting 3 a and 3|3 particles, llow
 276 Answer Key

ANSW ERS TO SELF TESTS

l.E 2.D 3.D 4. С 5. С ♦

CHAPTER 1
6.Л 7. В 8.С 9.Е 10. С
1I D 12.С 1З.Е 44.D 15.С
16.13 17. А 18.В 19.В 20. Е

CHAPTER 2 1. E 2. В 3. D 4. С 5. Е i *
6. С 7. А 8. С 9. А К). Е
11. В 12. Е 13. В 14. С 15.D * ?
16. С 17. D 18. А 19. D 20. D i
г

CHAPTER 3 1. D 2. Л 3. С 4. Л 5. С
т
6. С 7. D 8. Е 9. Л 10. Л
tf
1 1. A 12. С 13. В 14. Е 15. D
16. D 17.Е 18. D 19. С 20. D

CHAPTER 4 I. A 2. С 3. Е 4. В 5. С
6. Ё *7. D 8. Л 9. В 10. С
II.C 12. 1) 13. А 14. Е 15. С
-Л». 16. С 17. Е 18. Е 19. В 20. С

C H A R IE R 5 1. E 2. D 3. Л 4. С 5. В
6. С 7. В 8. Е 9. В 10. Е
1 1. E 12. D 13. С 14. А 15. В
16. В 17. В 18. С 19. С 20. Е
V
♦
C H A R IE R 6 I.с 2. Е 3. D 4. С 5. С
6. с 7. D 8. Е 9. В 10. С
II.C 12./К 13. 14. В 15. А
16. D 17. А* 18. Л 19. D 20. В .- J b
Y- 5 0 - <4 ЛЛ
ц < У
CHAPTER 7 J. В 2. В 3. Е 4. D 5. Е
“б. D . 7.А 8. Л 9. Е 10. С 1 . -■—------ '• —
, » 11 . D 12. В 13. С 14. D 15. D
16. E 17. В 18 В 19. В 20. Л

CHAPTER 0 l.E 2. Л 3. Л 4. D 5. D
6. С 7. В 8. А 9. С 10. В
1 1. В 12. В 13. А 14. Л 15. Е
16. В 17. I) 18. В 19. с: 20. Е
-354