Chemical Energetics

Standard Enthalpy of Lattice Energy:

EX0
ionic
for compounds Hess law

It is the 1m01
-

enthalpy change when .

of a
compound is
ions under standard conditions
formed from its
gaseous .

lattice Association dissociation it will be endo

a. K a
.

Energy if .

""
NaCl lattice is
Haig ,
+
clig ,
>
,s ,
*
energy a measure
of
ionic bond strength Energy .

""
2AlYg ,
+
304g ,
>
AK03 ,s , released when ionic bond
formed .

bond but is not

-
Lattice
energy explains strength necessarily responsible
ionic
for solubility or
melting point of an
compound .

Trend of Lattice Energy:

-

the ✗ 9++9
-

r++r
*
Down the Group
-
^

till the
1¥:* size ion ionic bond
of
× *
.
:
strength ,

NaCl
KC1 Kt ion has
larger radius than Nation
-

Rbcl Nat & Cl have

stronger electrostatic force attraction
of
-

✓ Cscl

* Across the Period

-
Metal Oxides
e.
g. " "

Na :O M50 Al :O;
the
of;;¥
×

'
*
Charge of cation +

radius cation
of
ionic bond
.
+
'

+
^
strength
HL .
E
Chemical Energetics
-3 "

the ✗ 9*+9
-

-
Na ;p ;5
Na Nice
☒+ r >

anion decreases
Charge
-
on .

Electrostatic attraction decreases

force of
-

the decreases .

Calculations using HessÕs Law:

"

i. Born Haber cycle :

>
Nation +
Cly
1st E. A
1st I. E

Hacks, Ii Na:* Clio

Haig
~
,
+
Clig^
,
>

1
r

1st Ionisation 1st electron Hatm Ct

Energy affinity Nƒ
"
Nags dig , t " "m "
^ ^
Na ,s, + { Cling ,
the
Hatm Hatm 0

Macs) ↳ Hf
Chug ,
r
Nacho ✓

Electron 1st E. A
Affinity
*
.

-
It is the
enthalpy change when 1m01 .
e- is added
to 1m01 atoms to 1 mole
.

ion
gaseous form mono
negative
gaseous .

exothermic
I e- Cl
Cly ,
+ >

;g ,

2nd E. A endothermic

It is the when 1m01 e- is added to

enthalpy change
-
.

1 mole mononegatiie gaseous ions to 1 mole

form
dinegatiie gaseous ions .

"" " """

The e- loses extra to the shell
of
-

energy occupy energy .

affinity
is to
repulsive force
Energy required overcome between negative
¥

ion and e- in electron

subsequent affinities .
Chemical Energetics
1st E. A + 2nd E. A =
endo

Trend of Electron AfÞnity:

* Across the Period *
Down the Group
-
Radius decreases .

E. A decreases
'

Nuclear charge increases Shielding effect

. .

Electron Distance blw Nucleus and

Affinity
- .

valence shell
Nuclear
force of attraction
-

.
"

Nat, +
Cly
is, I. £-
1ˢᵗ E- A
Hf
=

Hatm Na +
Hafm Cl, + 1st I. £
.
+

Nat ,
Nair Chigi 1st E. At the
^

Hatm Cl
tak
"

" "m Na
Macs, +
{ Clzig , ,
the
O "

Mojo
Hf : ^

v
Nacka .

Mg ,ji +0¥ ,

„
^
Mgᵗ?g ,
+
Qg ,
2nd E.
1st E. A
1st + 2nd I. £
Mg ;gf Oig
+
✓ ,
+
nagy , Digi
Hatm 0
the
V19 g) I 02191
+
,
^

Hatm V19
0 M9 is ,
+
I 021Gt
Hf
.

Nights ) v

odor
 Chemical Energetics
Polyatomic Ions:
Ca OH ≥
021g,
+
Hug ,
+ 2 e- > 201-1
-1g, -130

Hf
=
-1800 1st I. E =
470 the =

?
Hatm Ca =
+480 2nd I. C- =
1080

Ca ;) ; ZO1-1IG ,

470+1080

Cag ,
+
^
20 Hig , "

the =
-3700 KJMOI
-

130

+
Cag, n
02cg ,
+
Hugs H4E

+480

Cats + + H
0 021g )
2191

-1800

✓ Ca OH >
"
is,

Standard Enthalpy of Hydration: exo

High charge density

-

ions react with It is the ion is

enthalpy change when 1m01 of gaseous
-
.

water .
dissolved in water to
give infinite dilute solution .

physical process
-

02 > OH
;ag
,
*
Jon -

dipole attraction occurs ,

thus , Hnyd is EX0 .

19s
energy released

ions dissolve in
*

Only low -

charge density water .

Haig ,
-1
Chigi "r

Haig ,
>
Naia, Haig,
+
Clig ,
>

Naetaqi Cliaq ,
Hnyd / Nat)
-

Cl
y
'
Cliag ,
-

¥ Naia, -1 Clig , Hr =

Hnyd Nat +
Hnyd Cl

Hhyd IC1Y

Naetaqi Cliaq ,
Chemical Energetics
Trend of Enthalpy of Hydration:
Hnyd ×
9+ or
Hnyd ×
9-
r+
-

Down the Across the Period Hmd " aries

*
Group *

across the period

Hhyd ,

,g+z
_

µa+ µ Ay
"

remains constant
Charge Hnyd
.

Size Jon
of
-

Charge density Charge increases

- .

Ionic radius
Strength of Jon Dipole
.
- -

'

attraction .
.

Charge density
Jon Dipole
Strength of
- -

-3 " "
^

p s Cl
>
t
strength
-
decreases Hnydu
g-
decreases
-

Charge density .

Strength of Jon Dipole

- -

attraction .

Standard Enthalpy of Solution:

It is the when 1m01 substance is dissolved
enthalpy change of a
-
.

in water to dilute solution

give infinite .

Nachos, >

Natag ,
+
Cliag ,

* To determine Hsa we need a Thermometer , Polystyrene

,

Cup ,
Electronic Balance .
150Mt cop

Place a lid increase precision

*
Improvements :
of thermometer
,

increase precision electronic balance

of .

HS01 HHyd HLE

of a compound of an son
of a
compound
exo exo exo

endo
Chemical Energetics
HS01
Nally, >
Na[g) +
Cliaq , formation of aqueous
' >
formation of
ions lattice
>

HS01 HHyd HLE

= -

the Htiyd

Haig ,
+
Clig ,
Solubility Equation

Hso , 0 endo less soluble Hsu is ive

If
- *
more -

Hsu 0 EX0 more soluble compound is more soluble .

Hso NaCl
,

Method I Method II
" "

Hhyd Nat -390 KJMOI Hf NaCl -411 KJMOI

= =

- " "
-384 KJMOI Nat -240 KJMOI
ftp.ydcl Hf
= =

,aq,
" "
lattice dissociation 1-778 KJMOI Cl ;aq, -167 KJMOI
energy
=

Hf =

Calculate Hs Nacho ,
> Nat + Cl
,
loop tags

Hsa =

Hnyd
-

the Hso ,
=
-240-167+411
' I
778
-

=
-390-384 -

=
+4 KJMOI
'
= +4 KJMOT

Solubility of Group II Sulphates & Hydroxides:

^

size Hier
Besa ,ag ,
of cation Hnydv

Castle Down the both Hnyd & the decrease because the
;Ö:::: Basta
,s ,
-

size
the
of
making
group
cation increases But
.

Hsu endo
.

&
, Hnyd
Compound insoluble
decreases
,

more

Thus
than

,s ,
-
.

,
solubility
Rason, of SO42 decreases down the
group .

BE0H)
"

"" cation Hier Hn,d

¤
≥ is ,
④ .

My / OH12 ,

¡ƒ Ca / OH1 ≥ -
Down the
group .
both Hnyd & the decrease ,
because the
tags
E- sr(OH14
,
size
of cation increases But . , the decreases more than
Ba / OH )↳ Hnyd making Hsa EX0 & Compound soluble Thus
, _
.

,
solubility
RA0H) 01-1 increases down
; of the
group .
Chemical Energetics
HS01
Nachos, >
Nata, +
Cliaq
,
-
Hess law
reasoning behind

solubility
>
.

%¡ "

the
lattice dissociation
Had Hhyd more soluble
"

H less soluble
,

„aIg
,
+
Clig ,

Hnyd
Ions Gaseous Ions
Aqueous r
<

""' "" "

"

you said
Entropy, GibbÕs & Spontaneity
is disorder. A how disordered
Entropy a measure
of measure
of
-

a is.
system
·Number
of possible arrangements of the particles and their
energy in
a system.

H Gibb's is the net value and

exo more
feasible of enthalpy entropy change which
-

H endo feasible
less
explains feasibility of a reaction.

to the
Spontaneity refers feasibility of a reaction.
-

"

Entropy: S Imol"K
Sincreases
A disorder. l
measure
of s
*

randomeas
probstofion
AtOK, absolute zero,
entropy
-

a
system is zero.
of law
of Thermodynamics
Third law Thermodynamics
of at
The
entropy of a pure crystal
Zero Kelvin is zero.

values atr.t p.

Element Na He Graphite Diamond

SoJ mol"K" 51.2 126 5.9 2.6

Reactants ·
Products

H -
ive tive
Hess's law or exothermic endothermic

Experimental Method

S -

ive tive
Sp-SR entropy decreases entropy increases
Entropy, GibbÕs & Spontaneity
Factor affecting Entropy:
as Volume Gas S
of
✗
4
i.
Temperature .

Particles IN1-1TA lesser

2 .
#
of
✗
S s .

stronger the IIYFA ,

Mass as the S
3.
Physical state 6 .

How to determine sign of ΔS by observing a Reaction?

Matter
Physical states
of
em =
environment
'

EX0 Sen Nz ; 2MHz S ive

31-12,9
= > = -

,
, ,g,
Endo =
S
em
'
4m01 .
2m01 .

Semi
-

H ✗ 1000 CACO} >

CA0 +
CO2 ,g S = + ive
,s , (5) ,

T
0m01 1m01
.

gas .

gas

Question .

S= ive H five
Holes, > + =

HOW solids bond

liquids
breaking

GibbÕs Free Energy:

"
G KJMOI

It is the net value Hand S Which about

of explains feasibility
-

reaction
of a .

G= H -

TS

*
G 0 ,
reaction is spontaneous
*
G 0 ,
reaction is non
spontaneous
-

H S G
-

ive + ive + ive

work done
energy for
increases
exothermic entropy from system requires
:

R > P reaction is non spontaneous

+ ive -

ive -
ive
endothermic entropy decreases from system has
energy available for work
R > P done : reaction is spontaneous
Entropy, GibbÕs & Spontaneity
Spontaneous Reaction: feasible reaction

-
A reaction which its accord
happens on own .

Or

-
A reaction which does not external work
require
done .

4 Types of Chemical Reactions:

R > P exo endo + S -

S
, , ,

i. all
spontaneous at temperatures
ii.
spontaneous at low temperatures
iii. spontaneous at high temperatures
iv. non spontaneous at all temperatures

a. H = -

ive b. It = -

ive
S =
+ ive S = -

ive

G =
H -
T S G =
H -
TS
= -

ive -

+ ive =
five) T/ + ive/ -

= -
ive =
ive or + ive
-

Reaction is -
Reaction is spontaneous at low
spontaneous
-

at all temperatures . temperatures .

e. e.
g. '
g.
NaCl 21-12 N2G 2MHz
+
+
ftp.g 3h29
> >
Nag, , ,aq+ ,g, , , ,g ,

It =
-

ive H =
-

ive
S =
+ ive S = -

ive

* At low temperatures TS will be ,

a

smaller value than H a

making
and reaction
negative spontaneous .
Entropy, GibbÕs & Spontaneity
c. It =
+ ive d. H =
+ ive
S =
+ ive S = -

ive

G- H -

TS G -
H TS -

=
five -

T five = Hive) TI ive) -

-

=
five or -

ive = + ive

-
Reaction is
spontaneous at
-
Reaction is non -

spontaneous
at all
high temperatures .
temperatures .

e. e.
g. g.
Ca >
CaQs + C02 Graphite > Diamond
%, ,
,g,

H =
+ ive H =
+ ive
S =
+ ive S = -

ive

* At
high temperature TS will ,

be more
G
negative making
negative Therefore .

reaction is spontaneous .

Q In and H burn to produce CO and

.

oxygen graphite
excess
of
limited supply
, , ≥

H20 respectively In of .
a 0≥
, graphite burns to form
CO
only .

Write indicate which

a. an
equation including state
symbols to ,

these combustion is most to to lead positive entropy

of likely a
'

change Cess +3202cg Hug +

Cozy 1-40,9 T. i s+ 202cg CO91
'
> +
, , , , ,
.

2.5 gas moles 2 moles 0.5 1

b. Write
equation relating enthalpy change
an

and H t s
.
free energy
change entropy change G = -

i. In terms G what is meant the term

c.

reaction .
of G 0
, by spontaneous

ii. Consider reaction which at has + G & S

a a
given temp .
-

Will the make G less

increasing temp .

positive ? Explain .

No G =
H TS the will make
it becomes Increasing temperature
-

positive + ive H TI ive / T S positive

= - -

more .
-

more .
Entropy, GibbÕs & Spontaneity
② .
^

s
^

Temperature
100¡C

0¡C

10¡C >

Temp %

Standard Molar Entropy: so

It is the 1m01 substance in its standard
of of
-
a
entropy .

state under standard condition .

+
S
14204 ; ZN02 start S is ive
i
: +
I .
.

,
1GI + H
Equilibrium :
5=0

2 .
G =
H -

T S G via Hess's law

¡
CH4 + 20, >
CO≥ +
21-120
n n n

O
Gf 1 elements )
=

Gt Gf 2✗
Gf

GibbÕs Free Energy Change of Formation: ai

It is the Gibb's is
when
of 1m01
compound
-
a
energy change .

its elements in their standard states under

formed from
standard conditions .
Ionic Equilibria
Bronsted & Lowry Theory:
Arrhenius
Theory -

acid releases Hᵗ ions in Acid proton donor CH > CO0H +

H20 _
-

CH > CO0 +
Hit
Acid Base Base Acid
aqueous
solution
_
Base proton acceptor conjugate conjugate
base releases OH ions

solution A weak base acid vice

in
aqueous
*

forms a
strong conjugate & versa .

Lewis
Theory _

Acid e-
acceptor C21-6OH +
1-1,504 >
C21-1SOHE +
HS04
Base e- donor base acid

HF + 2- >
F- + HZ
in acid base
Conjugates only
-

reversible reaction .

pH Calculations:
Acid Base Weak Base
i.
Strong 3 .

Strong s .

2. Water 4 .
Weak Acid

Titration & Titration curves

Buffers
- -

Product ksp Partition

Solubility coefficient kpc
- -

pH Calculation of Strong Acid:

-

Hᵗ Cl is H+
HCl
of in
+
-3
> *
pH a measure
0.1 moldm solution
a .

0.1
pH -109,0
=
Hᵗ
100cm
's
H20
cone .

of
pH =
-

log ,
:H !
Calculate pH
of HCl
✓

Q .
a.
""
Calculate pH
b.
of HCl
after IH: =
10

r adding water
Hcliaq
-3
0.55 moldm +
-

HC1 H Cl pH
a > +
-109,010.551=0.260
=
>
soon .

-3

b.CN, =
C24, 0.55×50=4×150 ↳ =
0 183m01 dm
.

-109,010.183) pH I
✗
pH = *

IH:
Ionic Equilibria
Q Final Mixture
.

Hcliaql -3
Calculate pH of .

0.20 moldm
'
30cm
HC1 NaOH NaCl +
1-120,1,
+ >

tags of' tag

n =
6×10-3 3.75×10-3
N1-1CI → (6-3.75)×10-3
NA0H ;aq
0.15 moldm
,
-3
excess
limiting 1 :
I excess

}
25cm
i.
cone .
HC1 =
2.25×10-3 =
0.0409 mot dm
-3

55 Ö 1000

0.0409 1.39
pH -10g
=
>
,

Water:
It is autoionisabk H20, OH EH ? I0H?
pHof H
:{
-
*
Water has a
-
an
species _ =
.

;g,

7 at room temperature base acid

& pressure The pH

.
it? I0H? It? I0H:
these
changes if
conditions 14=1-1 OH ? Kcx 1-40 =
:HÖOH:
change .
.

IH20 .

" "
Ionic Product KµÖHÖOH ? 1.0×10 moidm at it
of Water >

.p .

Water Dissociation
constant

is 14, is an constant
P0H by temperature Adding
affected Does
-
a measure *

equilibrium is
.

Only .

:0H? acid :H ? base :OH? not

of > ✗ ✗ I
or concentration
affect Kim
. .

"" "" "

IH OH ? =
1.0×10 -1-1+-7=1.0×10 it? =
1.0×10
_
"
H1-4OH have same cone .

IH ? =
1.0×10-14 I0H? =
1.0×10

"

1.0×10 7 at room temperature

pH =

log
=
-

, .

Kµ=:HÖ0H ? log Kµ log :H? log :OH?

-

= -
+ -

+
pKµ= pH P0H pk #
=

-109kW
Ionic Equilibria
Q Dissociation endothermic
.

of water is .

How HI, OH
-
_ -1
:p
At 37¡C pH water is 6.8 Calculate Neutral 6.8 at 37¡C
of pH =
:
.

_
"
i. it? 10 pKµ KIN
iv. -10g
= =

'
" "
10-6.8
_

ii. I0H? =
10 y .
Kim =

-1-1 OH ? = .

10

iii. P0H =
6.8

it? I0H: Acid it! I0H: Base it! =

I0H: water
pH P0H pH P0H pH
=

P0H

kw-i.tl OH ? pKw=pH +
P0H

pH Calculation of Strong Base:

Alkali which dissociates in solutions
completely
-

aqueous .

*
Group I Hydroxides NaOH '
Nat + OH
-3
0.2 moldm 0.2

KwÖHÖOH?
""
10%-1-1? ✗ 0.2
PH -10910 IH ? 13.3
-109,05×10
= = =

.
"

it? =
5×10

Q B0H , is base
.
a
strong .

Write dissociation B0H

a.
equation of ,

133++301-1
-

B. OH ,
>

-3
Calculate pH 0.14 moldm B0H}
b.
of
""

I0H? 3×0.14 it? 1×10 IH ! 13.6

-10g
= = =

3×0.14

KwÖHÖOH?
Ionic Equilibria
pH Calculation of Weak Acid:
Alkali which dissociates in solutions
partially
-

aqueous .

CH3 OH +
H20 -
-

CH > CO0 + H }Oᵗ

-3 -3
0 I moldm
.
01 moldm

I 0.1 *
O O
R × *

E 0.1 -

✗ ≈ 0.1 *
✗ ✗

Water is constant , its

* a concentration remains
fairly constant .

He =
IH> COO? :H ? He ✗
IH20: =
IHsCOO-I.tt:
IH>COOH: -1-120 .
IH>COOH:

Acid Dissociation constant Ka =

ICH> CO0-1IH? IH> CO0? =
It?
IH>COOH:

it?
Ka Ka of 0-13001-1=1.51×10-5
=
*

IH>COOH:

IH ? =
1.51×10-5 EH ? = 1.23×10-3
0.1

CH3 OH 1.23×10-3 2.91

pH of -10g
= =

% Dissociation =
1.23×10-3 × 100 =
I. 23% weak dissociation
very
0 I
.
Ionic Equilibria
pH Calculation of Weak Base:
-

+
NH3 H20
-

+ _

NH4 + OH
O.IM ✗ ✗

Kc =
: NH4 OH : Kc ✗
IH20: =
I NH4 OH : I NH4: =
I0H:
IN1-1II-120: K, INH}:

's
K, I NH41-0HI I0H? Kb NH3 1.63×10 not dm→
of
= =

IYH}: INH; -0.1

-3

I0H: = 1.28×10-3 not dm Kim =

-1-1 OH ?

_
" -3 "

It? =
7. 8 7 × 1 0 mot dm pH
=

-10g 7.8 7 × 1 0 =
II. I

① .
a. Write dissociation
equation of CH3 1YH ≥ methylamine .

+ -

CH > NH2 +
H20 -
-

CH31YH >
+ OH

Write
b. Kb expression and state its units .

-3

Kb =
(CH3N-4TIOH ] = not dm
[CH3N H21

What is meant
c.
by pkb ?

pkb = -

log Kb
-3
d. Calculate 0.155 moldm CH31YH at ftp.pkb -4.58
pH of
-

_
""
"
10 =
Kb (OH -1--2.02×10-3 EH ? =

4.95×10

'

% I0H ] Kim :HÖOH: pH

=
it?
log
= = -

0.155

pH
=

11.3
Ionic Equilibria Buffers

acid
*
pH is not a measure
of strength of an or base .

That is its chemical properties

Acid dissociates Weak Acid dissociates

Strong completely partially
*
.
.

HC1 =
0.IM CH >CO0H =
0.IM

+ -
-

HCl > H + Cl CH>COOH +

H20 -
-

CH > C00 + Ht
2

0 I ka I I. 5 10-5 ✗
pH log
-
= = × =
.

=
I 0 .
, 0.7

*
A solution which will
-
Buffers:
react with H1-4OH ions addition
A solution which resists
pH change of small amount
of
-
on

acid or base added .

*
Contains acidic & basic that are maintained in
components
Their behaviour is
equilibrium .
amphoteric .

Acidic
Buffers Basic
Buffers calculations

/
no

weak acid basic salt Weak base acidic salt

' .
- .

Preparation of Buffers:
base to weak acid
I.
Adding some
strong a .

weak acid & basic salt

2.
Mixing of .
Ionic Equilibria
α. Adding some Strong Base to a Weak Acid:
-

OH
IH> COO? :H ? IH ! IH>COOH:
.

strong ka = =
Ka ×

""

CH >CO0H IH>CO0H: ICH> COO?

, ,
,
both sides
Taking log on

"
IH>COOH: ett
log :H! ka =pKa
: Acid:
t
tog pH log
-

log
- -

IH> CO0? I salt: > formed

Anion
pH
=

pka -110g i. Salt:

Acid:
*

of a weak acid is

-
its salt .

sake salt & acid

*
Volume
of mixture is
moles is the
for both
i. ratio
of ratio
of cone .

Calculation .

NA0H 0.30 not dm

-3
n NA0H =
0.30×0.04=0.012
'
¥
40cm 0.45×0.05=0.0225
n CH > CO0H =

CH > CO0H 0.45 not dm→

≥
50cm
NaOH +
CH3 CO0H -
i

NACH> CO0 + H20

s
-3
-

Ka =
1.51 ✗
10 mot dm

CH > CO0H 0.0225 0.012

n
left
-

/Salt] 4.82
.

pH pKa Ka
log Pka -109
. .
=
+ = =

[ Acid]

pH 4.82 0.012 4.88

log PH
=
+ =

0.0105

>
Q Na is added to 0.2 moldm ? 400cm HCOOH Calculate
.

0.69g .

pH of buffer .
pka =
4.68 & Ar
of Na =
23

Na + HCOOH >
HC00 Na + I2H ,

Na n HCOONa 0.69 0.03 pH 4.68 0.03

log
=
n
= =
= +

23 0.05

HCOOH 0.2×0.4 -0.03=0.05

n
left =D

4.46
pH =
Ionic Equilibria
β. Mixing Weak Acid & its Basic Salt:
CHe COOH
CHs 200 Na 0.5moldm's
3.9 Calculate
of Buffer.
V

Pa pH
I
=
0.8moldme"
40am"
40cm"
80cm" 0.8 x 40
4.8 + 8O
PH log CN
= =

242
8. 5x40
80
5.01
PH
=

A chemist
8. 200cm" 0.2moldm"
prepares a
buffer solution
by mixing of
HNO, with 800cm moldm" sodium nitrite, MaMOn Calculate the
of 0.0625
4.64x 18
-
pH of buffer solution. Ka =

HNO2 0.2 +0.2 PH logKa+log

: -

~
8.0
=

& NaNOz =0.8x0.0625

pH =
3.42

When Acid:=iSalt: then

↑

pH-pKa
When Acid:
↑
iSalt: then pH pKa

When Acid:
↑
iSalt: then pH pKa

①
CHe COOH
a Calculate pH. Ka= 1.51x10"
0. 145 moldm's

0.33 3.20
PH log(Ka) +
log
-
=

CHs200Na =

0.35 mol dm's

0. 145

A 0.015 moldm" Hel added

3. small amount.
of was ·
Calculate pH of buffer
after adding HC.

The acid added will react with the salt and

form acid in 1:1 ratio.
↑

PH pKa 0.35-0.016 5.14

log
= + =

0. 145 + 0.015
 Ionic Equilibria
Types of Buffers & Explanations:
H"+CHe200;
⑧

I.
>
CH, COOH CHeCOOH
OHCH,[00H <
2HsC08"+ H,0
>
CHz COONa

2H"+ CO,"
*O

11.
~
CO, +H,O or HCO,
>
NHa,COz OH NHy" >
NHs +
H2O

iii. Amphoteric salts.

onetype of
or -
HC, Ha
~react with H
NaHSOn, NaHCOs, NaH,POn, NacHPOn
with

totypes ofi EYRSOnFETYSoucreact HSOn + Ht H.SOn

HSO; +OH, sO,"+HO
>
HPO,+H-
HPOn"TOH
>
HePOn
1POytHeO
·

H,209 -
H+CO,"
-

HsPOy --H" + HcPOn #90'+Ht <

H,C03
threetypes of of HsPOn -H+HPO HCOz'+OHf ~
Co,"+HO
-

HsPOy --H +PO3

HcPOn +Ht >

HgPOn
HePO; +Of <
HPO,"<HO

R
iv.
HeN C COOH HeN CHe COOH
basic acidic
e.g. Glycine
H HeN CHe COOH + HT >
HeN" CHe COOH
HeN CHe COOH OH CHe CO8'+H2O
Amphoteria + -
HIN
Amino Acids
Ionic Equilibria
Weak Acid

stronger Acid relatively Weaker Acid

'

ki.pkau.it?:pH .
kau.pki.it?u.pH
O O
'

H C O H ka Kar CH
,
C O H
v v

weaker bond bond

stronger

Two Concepts:
i. and
e-
donating withdrawing groups
ii. delocalization

e-
Donating CH3 e-
Withdrawing
t.io .

NO nitro
alkyl CH3
* *
,

* ether *
CN
OH
Halogens
* *
donors
very good e-
*
NH2 * C. Acids
*
Ester
-

They create positive inductive *

Aldehyde
effect .
* Ketone

They create
negative inductive
-

effect .

Delocalisation: -

spreading of charge
Delocalization
Stability
- ✗

i. – ,– delocalization
– bond will delocalize with
another – bond at most one

a- bond Benzene
"

delocalized a- e- cloud
away .

'

C C C C C C C C C C C C resonance stabilized structures

610 350 610
"¡
610 610
Ionic Equilibria
i. P.A delocalization:
will delocalise with eat most atom
↑ er lone pair of e i one

away.
Inductive
O & Positive Effect
&
. .
.
.

CH, H, CH, 2 0 I resonance stabilized structures

Inductive
Negative effect
OH
SM.E,
CHaCHe sne,
ve h x

Conclusion:
Lone delocalizes into
pair of oxygen the
e
withdrawing increase benzene The CO appears
-

groups ring. but as a

acidity single bond has

strength like that

double bond.
decrease
of a

donating groups
-
e

acidity

0 Cl 0
1

8 8t

Chs; 2 0 If CHc C O If
<

Meaker acid stronger acid

ChH O HChO

If C C C0 H If C C C H

If If H

O O O

H C 0 H CH, C O If C O If
CH,CHe

HCOOH is the Acid in the C. Acid

series
strongest Carboxylic homologous

"The acid with induction is

negative effect stronger.
Ionic Equilibria
Carboxylic Acids:
O O O

H C 0 H CH, 2 0 If 2 0 If
CHICH,

decreases down the series

"Acidity
decreases increases.
homologous
*
Ko 3 pKa
0. O

"
Inductive
H C O H- ·H 0'+ H
effect
-

<
C
acid
stronger weaker base -
0 H bond
O O strength
-
Anion
a

Stability of
0+ H" Anion
CH,' a
Basicity of
-

a
CH, · 0, H -

acid
weaker
stronger base

"clts isanedonatinggroup, and createspositiveinductneed

CHSCOOH than H2O0H. CHsC00is a less stable anion and
due to positive inductive
has a

than in HCOOH.
greater negative charge effect
base than
1000;
Therefore,
CHSCOOH
CH3200
weaker
is
acid.
a
stronger
making a

HSOn: HY + HSO,"
HO CcHgOH
HSOg- H++SO,"

Itisdifficultfor
"
viele
H. COg =
H H20s"
+

# 0. H. H +0 H "

H.COs -
H C0s
+

As POn- HY + HPOn
CHs, 0. H H" +
CcHs 0" presentH" ions
Already
A
AsPOn--HY+HPO,"
-

H++POn" will the

AsPOn- reverse
equilibrium
H2SOn H" +
HSO,
8 IM 0.1N

·H "+SO," x187
H50;- Ka= 1.01

X X

9. Calculate x.

Calculate moldm"
ii. pH of 0.1
of H130,
Ionic Equilibria
Basic Buffers:
↑eak base - acidic salt

H "+NHs, NHnt

H+NHaY 'NHst HO
↑Hs-NH,"

HY +CHyNH, CHNH,t
H+CHNHg" sCHsNHst HO

CHsNHc"CHyNHs"

Titrations (Acid - Base Titrations):

strong Acid Neutral

- Salt
*
endpoint pH is determined 9 +
strong Base H
=
7
the salt present ii. Acid Weak Base AcidiaSalt
by Strong Acid +
pH 7
iii. Weak Base Basic salt 7
+
Strong pH
↑X. Weak Acid + Weak Base -
Neutral Salt H
=
7

STRONG ACIDS: INEAK ACIDS:

HCl, HNOs, HSO, H2COs, HsPOr, Carboxylic Acids
STRONG BASES: INEAK BASES:
1st Group OH; SrOH, Other OH; Aqueous Ammonia, Amines
BaOHe, RaOHc

i. Strong Acid/Strong Base Titration

HCL + NaOH ·
NaCl +HO

Acid ↑leutral Base

Litmus Solution red violet blue
red pink
Methyl Orange orange yellow
Phenolphthalein colorless colorless pink
Ionic Equilibria
>NaOH 0.2 moldm" =3.75x10
~ Hd =
0.15 x0I
Volume=?
x25 =mo,e
~

HCt 0.15 moldm

,

25 cm3 volume 3.75 =

x
10" · 18.75 cm
0.2

18.75cm NaOH is
required for complete neutralization.

8. Her 0.13 =0.024

Calculate pH of initially. IH 0.15 pH =-log
=

Calculate pH
8. 30am", 0.2moldm" NaOH.
of mixture
after adding
"

excess NaOH =
30-18.75 ~ NaOH =
0.2 x 11.25 =
2.25x10
1000

NaOH 2.23x10=0.0404
of
=
cone
551000

KN= H - IOH? iH 1.0 x 10 2.341184 12.6

pH
= =
=

0.0404

Pit

7
pH at
endpoint-pH at midpoint
a ·

10volume NaOH
of
added cm?
Ionic Equilibria
Titration Curves:
Ple pl Pit PA
endpoint asic Salt
*

7- endpoint Neutral Salt I a

T -
- - endpoint Neutral Salt

endpoint Acidic Salt

strong Acid
Strong Base Strong Acid Weak Base Weak Acid Base Weak Acid Weak Base
Methyl
Strong
in Litmus
litmus Phenolphthale

Acid Neutral Base

red pink
Methyl Orange orange yellow
red violet blue
Litmussolution
Phenolphthalein colorless colorless pink

How to choose indicator for a titration?

Endpoint pH should lie between the pH range of
-

indicator.

ii. Weak Acid/Strong Base Titration:

PH

>
NaOH ·salt+ excess base

·
Titration salt+He
7. region
- As
AS S
A
-
CHy C00H PH=pRac
Buffer Region
pH=pKa-logYA ↳
x
C base added
an

①.
·

Moon addedthe
CalculatepH of CHs200H before
. was

>
NaOH
0.2 moldm"
21 cm3

-
ii. Calculate pH of mixture
after titration.
-
CHy C00H
0.2 mol dm's

Ka= (HP
2cm3

i. 2.76
PH log(H]
= - =

0.2

i.n CH,COOH =0.2 x 25.3x10"mol. ~ NaOH =

0.2x21 =
4.2x18"mod
1000 1000

Acid =0.8 "10 Mol. 4. 2x10"

~
left =x13-4.21
4.2x10"mol.
x10
pH =pKa "log 0.8 10'
salt
formed
x
n =x

3,54
PH
=
Ionic Equilibria
pl pl pl pl
s

I a
- I a
I a
I a
a

Acid Base Strong Acid MeakBaseWeak Acid Base Weak Acid Weak Base
strong Strong Strong

when acid is added

Graphs
↑

from burette.

Solubility Product, Ksp:

OH' All are insoluble except group I, HHu", so", Ba, Ra
+

CO,"All are insoluble except group I, and NHy

o HCO; All are soluble

o Nos"A l lare soluble

Go Halides
so,"A l lare

All
soluble

soluble
except Ba?" Ca?" pb
=

=
are except Hg? Ag?appe
Sulfides All are insoluble except Ba?" Ca?" Mg2" NHu

Mace at
Nace,, "find solubility of utp

100.00
mass-beaker
of beaker 9 water 140.00
of beaker saturated
mass -
9
170.00
mass
of
+
solutiong
↑
At saturation point:
salt-ion NaCI"Na" +C
lag) cag) solubility ofsoluble Salt:g 100g of water

40g Salt Water

mass of waterreissolved 309 30 4O

X 100

water
x
759 100g of
=

per
Ionic Equilibria Solubility Product

Ksp Definition:
the insoluble salt. In moldi
This is used to
find solubility of an

AgCl, s

Add saltin small amounts

AgCl,iAglagit Cliage
*

very
to water. As soon as it

becomes saturated, stop 1.040"ol" 1/

e.g.
the salt. in 100cm
adding
1.0x70:100cm X 1.0 x
=

10 moldm'
X 1000cm :

...
Solubility of AgCl=1.0 "10" moldm"

Conclusion: concentration the

of
solubility of an insolublesalt isthe
BasOni Batson -Bats -

solubility of BasOn
-SO = solubility of BasOn

Ca*
Ca, POnz,si 3Capt 2PO,ag 3
=

solubility of CazPOn2
-

PO
-

2
== solubility of Ca, POnz

Ka=IAg*Cl moldi's
AgClsi AglagtCliag same as
Ksp
solids not written in Ka expression

iBa**SOn
BasOni Batson Ksp=

Mg, POnzisi 3Mg*2POnig Ksp= IMg. POn-modm"

①. Dissociation equation of AgCI AgClsi AglagtEliagi

Kop Expression Ksp: IAg* Cl.

calculateSolubilityof AgCl smodme

Ionic Equilibria
How much mass
of Agel is soluble in

"
I dme "10" (100 + 35.5) =1.42x10
i. 1
"9
9. Dissociation
equation of
PEa
PbEz is) -

& po

X X
lag) gjcage
kep expression Ksp==PhCIa
X

"
Calculate
solubility of ObIc Ksp"2.50x10

·x:=2x. =250x10x =
Ph? =1.04 "10"moldm"

Factors Affecting Solubility: Le Chatelier's

1. Te m p e ra t u re
endo
salt-aqueous high temp,"solubility
Temperaturemay increase decrease
solubility.
↑
or

Common Jon
2.
Effect come
effect
Will reduce the
always solubility.
↑

salt-aqueous
18" mokdm"
AgCes Agapt Cag Ksp=1.0 x

Ksp==Ag"ICI"
:

Solubility of AgCL=1.0x10"moldm"
-The common ion is the
Hace
come.
You add same

the that ion.

as new come
of
AgCes Agapt Cag

new EC1-Oas
new: Ag" willbethesenew solubilityofAgce
be new:A te
 Ionic Equilibria "=
1x 10 new:
Ag" 0. 1
Ksp=new:Ag"CI"
1 10"moldm
new:
Ag =

10moldmesolubilityas
↑ x
it

New solubility ofAgein 0.1xPackis1

8.
Write dissociation
eg. Kep expression for BasOn.

BaSOu,T.BaEt SOsa Ksp=/Ba"1/SO,"

a Calculate Bason in moldm" in water. Ksp=2x8-moddm"

solubility of
2 -
18 = (Ba"]/SO," x =
2x1010 "moldm"

3. Calculate Bason in
solubility of
·

. 0.1 moldm" Arc (SOn)s at the same temp, in (b)

"

190,"7 =
0.3 13" x 0.3:2x10 (Ba] =
6.67 x10
new
solubility

Partition CoefÞcient: Kpc

Polar solute dissolves
->

in polar solvent a non Polar Solvent Non Polar Solvent

HcO a Clu
e.g. e.g.
polar solute in non
polar solvent. Polar solute more soluble less soluble
e.g. NHs

Non Polar solute less soluble more soluble

Iz
e.g.

The mixture is shaken to 1)

↑caecocm?
*

20cm CCls
allow is to distribute partition

& Ho
itself by water siodine. &
is 100miiis

jooemi 1zags
·

Tocacen
I

Kpc or Ka =
=Ixcen): =
no units
: 12 lagi
Ionic Equilibria
Partition CoefÞcient:
It is the ratio solute in two immissible solvents based
of cone
of
-

on
solubility difference at
equilibrium.
0.1moldm" solution 20¡
D. 100cm?
of a
of ammonia
solvent and
in water at was

shaken with 50cm

of established.
organic
an
left in a
separating funnel
for equilibrium to be

at
Acocosportionif the aqueouslayer was runoffand titratedagains
acid. What is
of ~

two solvents at
the partition coefficient of ammonia between these

20¡C?
20: 1.88x10
~ NHy =
0.01 NH3 ag). NHe cost 100: X

HC 1.80 x 10" 4.4x10"

n
NHscag
=
n
=

~ NHs in 20cm" 1.88x10"

cag)"

& NH3 cos)" 0.01- 14.4 "101: 6x10"

(NHscap) =
4.4x18" (NHscos): 6x10" Kpc: (NHscos1) = 0.128
100 30
1000 1000
(NHscag)

onac ont a t i I HCl

soon
& ·

-coemaste
moles HC react:moles MHz in
aqueous
solution
Reaction Kinetics
A + B ~
C + D

Rate :A A.
TA'times
Rate Rate
-
a
"2 times -2 times a times -2 times -I time
-3 times "3 times -pimes "3 times "I time "3 times

Rate Order:
It is the power to which come reactant is raised to, in
of a an
-

determined rate
experimentally equation.
M + 2X + 34 ~
CA + 2B
and Order 1st Order zero Order

Overall Order = 3rd Order

Rate Equation: Rate a

M.ix: iy Rate a
M.ix."

reactant is not written in the rate

-Ifthat a
equation, Rate =

KM:"X"Rate Equation
means it is zero order.
moldmg" moldm's"

1st Order:
" "
rate
Rate a A: ·A:
gradient: rate
Rate =
K:A gradient: K
-
I
K =
S constant
0.5 -

Half-Life remains

rate constant
t'z
0.25-

In time
a cone
against graph
:A is do i
exponential if the
half life is
constant then it is 1st Order,
It is the time taken the to halved
if not, then it is and Order.
Half Life: its initial value.
for come be
from

2nd Order:
" "
rate
Rate a A. :A ~

does not remain constant

Half-Life
Rate =
K:A. gradient: K
t'z

gradient: rate

:A i
Reaction Kinetics
Zero Order:
" "
rate
Rate a A. ·A:

Rate =
K:A:

Rate =
K

reactant has
effect the rate.
Changing of
↑
come no on

Factors Affecting Rate Constant:

1. Temperature ~

Rate =
1X K =
Rate
(K =X
Temperature

2. Concentration

c remains constant

-Rate Kix. Does not the

affect rate constant.
=

3. Pressure only for gases

KPx==Rate value rate constant remains the same

of
no
effect of pressure on K.

4
Catalyst
~

Rate
K increases the value
of K, the
↑

Catalyst as
=

=X rate increases.

For order ['c

first rate
equation: =Ine
↑
Reaction Kinetics
Using Experimental Recordings to Þnd Rate Order:
FIN16 P4Z 04 A +

B -C+ D
T12
↑ Pue 02
Experiment I 2 molder 4 moldi
Experiment 2 2 moldermoldin

TA:
B
n

2
Let's tic is constant Initial Rates Method is
* 2

say
:It is 1 Order A to
w.r.t to
t
employed find out the A
Rate C.A.
rate order
of B.
A
·rate We will how
B A
at t =
0
find
with the
x X

r
changes passage
R
ate kA: =B: time when B is
of
=

t'c method" vinitial rates method added

*5 17 P42

ammonia. white
Add
AgNOs, followed by aqueous Mall
forms ppt.soluble
in NHs
capi
Nat
forms yellow ppt. insoluble in
NHscag
Electrical
conductivity decreases as reaction
progresses, due to a lack
of
free charge carriers lions).

2-chlorobutanepri and in controlled

waterbath at 40%. known volumes
Nations are
kept an
electrostatically
are mixed solutions
both
with an electrical conductance meter inside.
of
together Stopwatch is
started the solutions mixed. Note electrical
as soon as are

conductance
conductivity
at
equal time intervals. A
graph of against
time is drawn.

T12
↑ P4202 .

dot-cross
In
diagram, more
electronegative element achieves
stability
↑
a

octet is incomplete, form dative bond.

first.If dative bonds.
erase
If it remains incomplete,
 3 For
Examiner's
Use
2 (a) What do you understand by the term order of reaction ?

.................................................................................................................................... [1]

(b) Cyanohydrins can be made by reacting ketones with an acidified solution of sodium
cyanide.
(CH3)2C=O + H+ + CN– → (CH3)2C(OH)CN

In a series of experiments, the reaction was carried out with different concentrations of
the three reagents, and the following relative initial rates were obtained.

experiment [(CH3)2CO] [H+] [CN–] relative initial rate /

number / mol dm–3 / mol dm–3 / mol dm–3 mol dm–3 sec–1
1 0.020 0.060 0.060 1.00

2 0.020 0.050 0.050 0.833

3 0.020 0.050 0.060 1.00

4 0.025 0.050 0.050 1.042

(i) Use the data in the table to deduce the order of the reaction with respect to
Ist Order
propanone ....................................................
zero Order
hydrogen ions ..............................................
1st Order
cyanide ions .................................................
(ii) Hence write a rate equation for this reaction.
Rate =

k/CN')/Propanone]
..................................................................................................................................
Two different mechanisms have been suggested for this reaction

Mechanism A: (CH3)2C=O + H+ → (CH3)2COH+

(CH3)2COH+ + CN– → (CH3)2C(OH)CN
slow
Mechanism B: (CH3)2C=O + CN– → (CH3)2C(O–)CN
(CH3)2C(O–)CN + H+ → (CH3)2C(OH)CN
(iii) Which mechanism is consistent with the rate equation you deduced in (ii), and
which step in this mechanism is the slower (rate determining) step? Explain your
answer.
↑
Mechanism B is consistent with the rate
..................................................................................................................................
The
equation. first step is slow step. It is zero
..................................................................................................................................
order w. r.t (HT] it is not a
.:
part of slow step.
..................................................................................................................................
since it is 1st order w. r t
cyanide a
they
..................................................................................................................................
propanone,
[7]
slow
are part of step [Total: 8]

© UCLES 2005 9701/04/M/J/05 [Turn over

Reaction Kinetics
Relative Order:
0N 2000 PU Relative order is
-

always assumed at start it is carried

added.

Relative order is the in the mechanism.

occurence
of a particle
-

Sampling Practical:
CHzCOCHs +In icCHyCOCHzl +HI
-rate order?
Ht
-
sodium
Thiosulfate

CHgCOCHg I
↓
S
I I

Is
155 30s 455 60s 755

NaHCOs
Quenching Agent
 4 For
Examiner’s
Use
2 In the late 19th century the two pioneers of the study of reaction kinetics, Vernon Harcourt
and William Esson, studied the rate of the reaction between hydrogen peroxide and iodide
ions in acidic solution. Relative order is always assumed at start it is carried
added.
H2O2 + 2I– + 2H+ 2H2O + I2

This reaction is considered to go by the following steps.

step 1 H2O2 + I– IO– + H2O

step 2 IO– + H+ HOI

step 3 HOI + H+ + I– I2 + H2O

Relative order is the
The general form of the rate equation is as follows.
occurence
of
-
a particle in
rate = k[H2O2]a[I–]b[H+]c the mechanism.
(a) Suggest how the appearance of the solution might change as the reaction takes place.
colorless to brown.
.................................................................................................................................... [1]

(b) Suggest values for the orders a, b and c in the rate equation for each of the following
cases.

numerical value
case
a b c

step 1 is the slowest overall I I O

step 2 is the slowest overall I I I
step 3 is the slowest overall 2 2

awat? Relative Order

for last step" is stoichiometric moles
A study was carried out in which both [H2O2] and [H+] were kept constant at 0.05 mol dm–3,
[3]

and [I–] was plotted against time. The following curve was obtained.

0.001
0.0009
0.0008
0.0007
0.0006
[I– ion] / mol dm–3 0.0005
0.0004
0.0003
0.0002
0.0001
0
0 30 60 90 120 150 180 210 240 270 300
time / s
© UCLES 2008 9701/04/O/N/08
 5 For
Examiner’s
Use
To gain full marks for the following answers you will need to draw relevant construction lines
on the graph opposite to show your working. Draw them using a pencil and ruler.

(c) Calculate the initial rate of this reaction and state its units.

Gradient
of tangent

moldms"
rate = ........................ units ....................... [2]

(d) Use half-life data calculated from the graph to show that the reaction is first order with
respect to [I–].
0.001 -0.0005 90 sec

0.0005 0.00025 180 sec

t2 is constant.
.................................................................................................................................... [2]

(e) Use the following data to deduce the orders with respect to [H2O2] and [H+], explaining
your reasoning.

[H2O2] / mol dm–3 [H+] / mol dm–3 relative rate

0.05 0.05 1.0

0.07 0.05 1.4

0.09 0.07 1.8

Rate <(HcOc]'CH +Y*

..........................................................................................................................................

..........................................................................................................................................
Ist Order
order with respect to [H2O2] = .....................................................
Zero Order
order with respect to [H+] = .....................................................
[2]

(f) From your results, deduce which of the three steps is the slowest (rate determining)
step.

Step 1.
.................................................................................................................................... [1]

[Total: 11]

© UCLES 2008 9701/04/O/N/08 [Turn over

 4
For
2 Nitrogen monoxide, NO, is formed in a reversible reaction when air is heated to the temperature Examiner’s
of a car engine. Use

(a) (i) Suggest a ‘dot-and-cross’ electronic structure for nitrogen monoxide.

N: 0*

(ii) The enthalpy change of formation of nitrogen monoxide is +90 kJ mol–1. What is the
enthalpy change for the following reaction?

2NO(g) → N2(g) + O2(g)

160
∆Hr = ..................... kJ mol–1
-

(iii) Explain why nitrogen monoxide is formed in the car engine.

Nitrogen oxides form due
Due to
high temperature. to
high temp. 2 lightening
....................................................................................................................................
strikes.
(iv) Using bond enthalpy values from the Data Booklet and your answer in (ii) above,
calculate a value for the bond energy of nitrogen monoxide.

bond energy = .......................... kJ mol–1

[5]

(b) At 800 K, nitrogen monoxide reacts with hydrogen according to the following equation.

equation I 2H2(g) + 2NO(g) → 2H2O(g) + N2(g)

The following table shows how the initial rate of this reaction depends on the partial
pressures of the reagents.

experiment p(H2) / atm p(NO) / atm initial rate / atm s–1

1 0.64 1.60 1.50 × 10–7

2 0.64 0.80 3.75 × 10–8
3 0.32 1.60 7.50 × 10–8

(i) Find the order of the reaction with respect to each reactant, explaining how you
arrive at your answer.

EXp1.N.r.t pINO) and Order

....................................................................................................................................

....................................................................................................................................

EXp3. w.r.t pCtcl Ist Order

....................................................................................................................................

....................................................................................................................................

....................................................................................................................................

© UCLES 2012 9701/43/M/J/12

 Reactants that appear in rate must be present
equation,
in rate 5
equation. For
(ii) Write down the rate equation and the units of the rate constant. Examiner’s
Use
Rate =

Kp(Hc) p(NO)"
....................................................................................................................................

The following mechanism has been put forward for this reaction.

step 1 NO + NO → N2O +I
O CHc+2NO,2HcO +Nc
step 2 H2 + O
-
→ HO

I
2

step 3 H2 + N2O → N2 + H2O

(iii) Show how the overall stoichiometric equation I can be derived from the three
equations for the individual steps given above.
NO O used and
are
being up regenerated
·
3NO +CHa <CHcO+He
(iv) Suggest which of the three reactions in the mechanism is the rate determining step.
Explain your answer.

Step 2 is the slow because it has Hc, and

step
....................................................................................................................................
is
coming from the
first step.
....................................................................................................................................
[8]

(c) The following information on half-reactions relates to the reaction between HNO3 and an
excess of FeSO4.

Fe3+ + e– → Fe2+ E = +0.77 V

3H+ + NO3– + 2e– → HNO2 + H2O E = +0.94 V
HNO2 + H+ + e– → NO + H2O E = +0.99 V

(i) Suggest the formula of the nitrogen-containing final product of this reaction.

....................................................................................................................................

(ii) Write an equation for the formation of this nitrogen-containing product.

(iii) Nitrogen monoxide forms a dark brown complex with an excess of FeSO4(aq).
What kind of bonding is involved in the complex formation?

....................................................................................................................................

(iv) Suggest a formula for this complex.

....................................................................................................................................
[4]

[Total: 17]

© UCLES 2012 9701/43/M/J/12 [Turn over

 4

2 Nitrogen monoxide, NO(g), reacts with hydrogen, H2(g), under certain conditions.

2NO(g) + 2H2(g) N2(g) + 2H2O(g)

(a) 'H¿QHWKHWHUPrate of reaction.

change in the amount

of reactant per unit time.
....................................................................................................................................................

.............................................................................................................................................. [1]

(b) Identify a change in the reaction mixture that would enable the rate of this reaction to be
studied.
in unit time.
Change pressure of
..............................................................................................................................................
gas per [1]

The rate equation for this reaction is given.

rate = k [NO]2[H2]

The result of an experiment in which NO reacted with H2 is shown in the table.

initial [NO] / mol dm–3 initial [H2] / mol dm–3 initial rate of reaction / mol dm–3 s–1
2.50 × 10–3 2.50 × 10–3 1.27 × 10–3

(c) Use the data and the rate equation to calculate a value for the rate constant k.
Give the units of k.

k= 1.27 x 10" =81280 mol"dm'st

12.5x10")" 12.5x10")

81280
k = ..............................
"
molidm's
units = ..............................
[2]

(d) A second experiment is performed at the same temperature. The initial concentration of H2(g)
is 4.60 × 10–3 mol dm–3. The initial rate of the reaction is 2.31 × 10–3 mol dm–3 s–1.

Calculate the initial concentration of NO(g).

2.44x10-3 mol dm–3 [1]

initial concentration of NO(g) = ..............................

© UCLES 2018 9701/41/M/J/18

 5

(e) State the order of the reaction with respect to NO(g) and with respect to H2(g), and the overall
order of the reaction.

[NO] 2

[H2] I
overall order 3
[1]

(f) The reaction is believed to proceed in three steps.

1 2NO N2O2

2 N2O2 + H2 N2O + H2O

3 N2O + H2 N2 + H2O

(i) Deduce which of the three steps is the rate-determining step.

Step 2.
....................................................................................................................................... [1]

(ii) Explain your answer to (i).

#)contains He 5 NOu is coming from step 1.
.............................................................................................................................................

.............................................................................................................................................

....................................................................................................................................... [1]

2nOu +6H" +S(COcH), '2Nn +IOCOr OH,O

© UCLES 2018 9701/41/M/J/18 [Turn over

 6

(g) A third experiment is performed under different conditions. A small amount of H2(g) of
concentration 0.0200 mol dm–3 is mixed with a large excess of NO(g). The concentration of
H2(g) is found to have a constant half-life of 2.00 seconds under the conditions used.

(i) 'H¿QHWKHWHUPhalf-life.

.............................................................................................................................................

....................................................................................................................................... [1]

(ii) Use the axes below to construct a graph of the variation in the concentration of H2(g)
GXULQJWKH¿UVWVHFRQGVXQGHUWKHFRQGLWLRQVXVHG

0.02

[H2] / mol dm–3

0.01

0
0 1 2 3 4 5 6
time / s
[2]

(h) NO(g) acts as a catalyst in the oxidation of atmospheric sulfur dioxide.

(i) Give two equations to describe how NO(g) acts as a catalyst in this process.

equation 1 ...........................................................................................................................

equation 2 ...........................................................................................................................
[1]

(ii) Explain why NO(g) can be described as a catalyst in this reaction.

.............................................................................................................................................

....................................................................................................................................... [1]

(iii) Describe, with the aid of an equation, an environmental consequence of the oxidation of
atmospheric sulfur dioxide.

.............................................................................................................................................

....................................................................................................................................... [1]

[Total: 14]

© UCLES 2018 9701/41/M/J/18

 0 level is a
pre-requisite
for this chapter
Electrochemistry
Electrolysis: endothermic

Decomposition of a
compound electrolyte
tively charged -ively charged into its elements by passing electricity
it.
e-lost
e-gained through
O xidation Reduction

using inert electrodes, contain

Performed
-

soluble salt

of anode freee. Graphite, Carbon, Platinum

Rules: 1.e-will
flow from anode to cathode.

Anions at anode cations

2.

at cathode.
discharge discharge

3. In
electrolysis of concentrated solutions, Halide
ions are
discharged. In dilute solutions, OH
ions are
discharged.
4. SOn" NOs never
discharge.
Electroplating:
Plating lesser reactive metallic surface onto
object
-

a an

by using electrolysis.
Anode: Ideal Case

Agis, 'Agate loss in mass

of anode
=

Cathode: in cathode
-
gain mass
of
Agate Ages
 Electrochemistry
In electrodes
reality, exchange in
is not
mass

due
of during electroplating
silver
equal because to
gravity, some
falls off
cathode into the
from electrolyte.
 Electrochemistry
Use of Electrolysis to Calculate AvogadroÕs
Constant (L):
Initial Mass
.
Stopwatch
of Cathodeg
Final Mass
of Cathodeg
CO
Mass
of deposited N

Current A I

Time s f

&
loss
of anode
uantities that be
can
be considered too.
Measured in
1. Nass
Electrolysis: Alternatively, mass can

Volume
2.
of Gas

1 .
nCu deposit =
m 2. Co" + 2e", Cu
63.5

3.2 mol.e.: 1 mol. Co 4. X =

2m Mol. e
X :
M63.5 Cu 63.5

1.6x10"C
=

3. To t a l 2m ( 2n x1
#ofe 6.
Charge
=
x

63.5 63.5

①= If
7.
=>
2mL 1.6x10" =
H L = 63.5H
63.5 2 m 1.6x10"
 Electrochemistry
Calculation using Gas Volume:
Stopwatch
-A
. Anode:
he
1 1 1 1 1
I I
40H '2HcOntOr
< -

Cathode:
Dilute HeSOn 2H+ + 2e-> H21g
lag)

Graphite Electrodes

Gas at Cathode cm3

Initial Volume
of Syringe
Gas Cathodecm3
Final Volume
of Syringe at

He collected am3 Y
volume
of
Current A I

time s f

nHc Y Imol He: 2 Mol. e-

=

24000 Y -
X
24000

x 2Y No. 2XL
mol.
of
=

e =

24000 24000

2XL 1.6x10" L 240001

Charg
=
e = x

If 24000 2)1.6x 10"

 Electrochemistry
FaradayÕs Constant:

Measurements needed to Calculate L:

Mass or volume F Le
of gas
=

1.

2. Current in ampere F
=
6.02x10" 1.6x10"
3. Time in seconds
 Electrochemistry
Constant: 1 mol. 2
Faraday's charge on

Constant: in 1 mol substance

Alogadro's #of particles of a

Variables to be Calculated:
Constant,use of charges
1.
Axogadro's concept

2. Mass deposited
3. Volume
of Gas
4. Time Use
Faraday's Constant
5. Current
Oxidation state metal ion
6.
of
0. 2A current
flows for 10 mins
through ag. HaSOn Calculate
volume
of He produced at r.t.p.

0: 2x10 x
60: 1200 C 2H+ + 2e> Ha

1mol. 2:96500 i
n Hc 0.012:2=
=

6.2x103
X :
1200

nHc =

too
.

1
= 0.012 mol.e
Y 144cm3
=
 Electrochemistry
Half Equations: oxidation reduction

e
1.
Charge
Oi+Se+BH"
↑ <NIn
2+
+4HzO
Reduction 2.Oxygen Here
Q.
20 +6e + IH c2Cr +FHsO

Or +2e+ 4H
↑
+
- Nn" + 2HcO
+2 +4

HCOOH ·CO2 2e +
+

2HF
-
3 +5

Hat
↑ + 3HcO >
No," +10H +Be

+S

N0s" +2e+ 3H+ ·

HNOz +
HeO
+C +
4
T

50," + 2e+ 4H -
SOct 2 HzO

+ 2.5

S10, + 0.Se -250,-

Redox Equations: e-gain e-loss =

Balance
half equations using e-cadd simultaneously to

obtain redox
equation.
↓nOu+BH +5e Nn" +4HcO
· x2

S0z + 2HcO -
SOn" +4H+2ex 5

2MnOn+5SOz +2HcO '2Mn" +5SOc"+hHT

 Electrochemistry
N0s" +10H" + Be', NHn"+ 3HcO
-

Sn < Sn"+ 2e x4

N0s" +10H + 4Sn -NHa"+4Sn" +3HcO

How to balance Redox equations:

2Nn0x + 5SO2 + 2 HO ·
2Nn" +
5SO," +GHT
+2
-

7
+
+ Se 2t
2xn ·2xn
+ 3+ 2e- +

5g4 -5g6
-

NOi
↓
+2. 5HcO 3HT · INn" +2.50;+4H,O

+7 + Se
↑(n 3 n2t
↑

3+-
50 e,500

Note: HcOc may act as a

reducing oxidizing agent.
0.A
R. A
HcOc -00
o xidized
R. A
0.A
HcOc -
HeO*
reduced
 Electrochemical Cell
Electrolytic Cell Electrochemical Cell
V

701.10X
-

1
ve-
e

Anode Cathode
-1
e ~
e-
more reactive less reactive
Zr Co
-
#

oxidation + 2
reduction
zn +
H + -

zn zn" 2e-
+ 2H 2e
+

>H2
1
dil. H2SO4

Anode: oxidation
+
Anode: oxidation
Cathode: -

reduction Cathode: A reduction

In the example above,

In Co have a potential
called Standard Electrode
Potential, SEP
of In
Reactivity Series

SEP
of CO.

The the separation

greater
-

in the reactive
of elements
the the
·t
series, greater
Potential
difference.
 Electrochemical Cell
Standard Electrode Potential: SEP

> E-
2m¥ "
zn
I

✓
"

Zinc rod Zn
gives
Zn"+2Ž Zn
'
.

The
difference
+
-

potential
"
bw
¡
+
+ t -

+ = +
Zn & Zn
species is C- +
+ +
+
_

+ +

V -

✗ Zn" + 2Ž .
'
Zn + ✗ V
Oxidation Reduction
Potential Potential
¡ "
standard conditions
[{ ✗idation [ 248k ,
1- atm ,
-3
1- moldm

Potential
oxidation states
difference alwayselement rises bw two
different
of an .

This is known
charge bilayer
-

+
E- ++
Helmholtz
layer
+
+ - + as .

+
+ IF
+ +
+ +
 Electrochemical Cell
:ƒ
¥ Redox
Equilibria
say
established

agag
.

gag
8
graphite or
pt .

<

g£ƒƒzn+ zn
Fe
"

Fest
Ct
2191

graphite orpt .

£
ƒƒ Not Iron electrode as

you introduce a
third
oxidation state SEP
reduction potential

£
^
"
ZN2Y-2EI
-

Zn Fe"+1ei Fe Cl, -12in 2cL

- -

×"
1st tag
tags tag tag (g)

Standard Hydrogen Electrode: 5. H .

E

-
21-1++2 e- .
'
H, 0.0011

cell

ƒfe
"

2Hᵗ+2Ž
AgttŽ
'

H,
Agis
-
-
.

,
lagl
 Electrochemical Cell
Standard Electrode Potential:
It is the potential
-

difference -3
between the test electrode
in a solution 1m01 dm & standard
of .

hydrogen
electrode under standard conditions
4 1 mot dm
.
-3
solution .
of 298K , 1- atm .

Reduction Potential SEP

Galvanic
cell Electrochemical Cell
21-1++25 it≥
.

is reactive
µ
AgttŽ -
'

Agis ƒfen Hydrogen more

,
H
Na
from
"
"
& e- move >
Ag
ca
H, 21-1++2/5
'

Mg '
-

A1 +2¢
2Ag
>

Zn
2AG
Fe
2^-9++1-1 ,
>
ZH4-2AG
Sn ✗11=+0.804

Pb
Elements reactive than have
H
hydrogen
-
more a

to value 4 vice versa

co
negative .

Ag '
increase down the
Au Values
of E series
-

increase
reactivity
.
from -

ive to live
after Hydrogen

Simple Construction of Cell: ¡

C-
Co "+2Ž .
-
CU +0.344
-
Anode cathode
Clz +
2Ž .
'
2cL +1.3611

more +ive -8 tends

to reduce .

E%= reduction -
oxidation
=
+1.36 -

+0.34
=

+1.0211 oxidation
reduction
" -
"
CU > Cu +2¢ CU1-2CL >
CU +
C12
-

2CI +2¢ '

CL2
Redox
Potential E%= +1.0211
 Electrochemical Cell
Question. EYel=1.25Y

Salt
Bridge -

0.76Y

Entze: - zn
(S)
lagi

Metal M Zinc
Cathode Negative
Red. Electrode
Anode
1mol.dm' N** 1 mol.dm' In OX.

Calculate EP M*M value.

zn, In+ 2e Ecell:Ereduction Eoxidation

-

"M* M:0.49
= 1.25 =1 X --0.76
 Electrochemical Cell
-

Whenever we have two ions in the cell, we use

inert electrode.
piece of filter paper or
agai
Salt Bridge: get soaked in soluble salt

solution
e.g. Naliagi, NaNOsiagi
etc.

Anode Cathode
more reactive less reactive
Zr Co
oxidation reduction

2e
-

zn zn" 2e-
+
2H H2

Anode: oxidation
Cathode: A reduction

-
+

Initial Zn* 1S0n:

:
=

(v2 =
s0n--
electrically
neutral electrically neutral

':

Progress:Zn*:IS0n: Cu IS0n -

Salt ions in the cells a makes

bridge generates half
-

that
solutions neutral so
electrically e-flow is not
hindered the circuitis complete.
 Electrochemistry
E values under Non-Standard Conditions:
:

=
5 moldm's E increases
more positive

0.5 moldm's E decreases

negative
more

Nernst Equation: >constant

Reduction Potential under
④

Non Standard conditions

the
#
of - in
half equation
is used variable
Equation on
half equations a cone.

For solid 1is written the

in Nernst
gas,
as conc.
of species
Equation.
Question a Calculate Ecell
Salt
Bridge
[0: 0.77-1-2.711:3.481
Na Pf
A B
b. State the effect if any on

Exel when:
i. NaNOs is added to
IM
NaClag
0.77
IM FeClg
-
IM FeClc
2.71
half
cell A.
b. i. Decreases. ii. He is added to
ii. No
change. cell A.
half
i. Increases. ·op Move Fells is added to
cell B.
half
 Electrochemistry
Question is 1.0+10"mol dm's
of AgCl
< <
Ksp
Bridge
Salt

i. Calculate (Ager]
iCalculate
K EAgAg
Ag An
ii Calculate Ecell
anode a cathode
iv.
Identify
··
AgCles Imoldm' KClag
a direction
of flow.
a

We reaction by Ka water
ignore

9. 1.0 +10
AgCl-Ag+Cl (AgfCT]
=

1.0x10'
(Ag] (Agel)
=
same as

i. 2 0.80 10 0.505
0.05Plog 1.0,
=
+
=

ii. (cell 0.505-1-2.P2)

=

How E explains Feasibility of a Reaction:

cell

G
I reaction is spontaneousentaneous
EO O
feasible
EO O not
feasible
If EO2 the reaction does notoccur, ithas a

high Enenergy of activation.

 Electrochemistry
① Will K reactwith AgNOs?
A metal reacts with a metal ion
+

oxidizes K
Ag ,?
+

+
k +e K
-

2.92X
+ .

e
Ag .

Ag +0.001
Identify which species oxred
time
reduces regardless of more

[0
+

(p 0.80
=
--

2.42 K = k +e
=
3.721 reaction is
feasible Ag+ ,
Ag

9. En+CUSOn'? Ente: · En
universal · Will Zinc react
w/ blueCotthe: ·Co pink universal reaction
Copper isolate? Cv" +e..CO" colorless
blue

(p 0.34
= --

0.76
1.10V
feasible
= +

acidic excess dil H.SOn

⑦. KMnOy +SO, ?
acidified
MnOne ... MnOqT,blacksolid
neutral ,

alkaline KMnOu limited excess, MnOn +4H++3e- -Mn0 + 2H,0

+0.17X MnOn't OH++5e: Mn" + 4H,O ·

acidified KMnOn acid in excess ·

purple colorless

SOn" + 4H + 2e= -

SO, +2H20 1.52 X

+

Exp 1.52 =
-
0.17
Cambridge Pre-U Revised Syllabus

o
4 Standard electrode potential and redox potentials, E at 298 K (25 C)

For ease of reference, two tables are given:

(a) an extended list in alphabetical order;

(b) a shorter list in decreasing order of magnitude, i.e. a redox series.

(a) E in alphabetical order

Electrode reaction E /V

+ –
Ag + e Ag +0.80
3+ –
Al + 3e Al –1.66
2+ –
Ba + 2e Ba –2.90
– –
Br2 + 2e 2Br +1.07
2+ –
Ca + 2e Ca –2.87
– –
Cl2 + 2e 2Cl +1.36
+ –
2HOCl + 2H + 2e Cl2 + 2H2O +1.64
– – – –
Cl O + H2O + 2e Cl + 2OH +0.89
2+ –
Co + 2e Co –0.28
3+ – 2+
Co + e Co +1.82
2+ –
[Co(NH3)6] + 2e Co + 6NH3 –0.43
2+ –
Cr + 2e Cr –0.91
3+ –
Cr + 3e Cr –0.74
3+ – 2+
Cr + e Cr –0.41
2– + – 3+
Cr2O7 + 14H + 6e 2Cr + 7H2O +1.33
+ –
Cu + e Cu +0.52
2+ –
Cu + 2e Cu +0.34
2+ – +
Cu + e Cu +0.15
2+ –
[Cu(NH3)4] + 2e Cu + 4NH3 –0.05
– –
F2 + 2e 2F +2.87
2+ –
Fe + 2e Fe –0.44
3+ –
Fe + 3e Fe –0.04
3+ – 2+
Fe + e Fe +0.77
3– – 4–
[Fe(CN)6] + e [Fe(CN)6] +0.36
– –
Fe(OH)3 + e Fe(OH)2 + OH –0.56
+ –
2H + 2e H2 0.00
– –
2H2O + 2e H2 + 2OH –0.83

– –
I2 + 2e 2I +0.54
+ –
K + e K –2.92
+ –
Li + e Li –3.04
2+ –
Mg + 2e Mg –2.38
2+ –
Mn + 2e Mn –1.18
3+ – 2+
Mn + e Mn +1.49
+ – 2+
MnO2 + 4H + 2e Mn + 2H2O +1.23
– – 2–
MnO4 + e MnO4 +0.56
– + –
MnO4 + 4H + 3e MnO2 + 2H2O +1.67
– + – 2+
MnO4 + 8H + 5e Mn + 4H2O +1.52
– + –
NO3 + 2H + e NO2 + H2O +0.81
– + –
NO3 + 3H + 2e HNO2 + H2O +0.94
– + – +
NO3 + 10H + 8e NH4 + 3H2O +0.87

7
Cambridge Pre-U Revised Syllabus

Electrode reaction E /V

+ –
Na + e Na –2.71
2+ –
Ni + 2e Ni –0.25
2+ –
[Ni(NH3)6] + 2e Ni + 6NH3 –0.51
+ –
H2O2 + 2H + 2e 2H2O +1.77
– – –
HO2 + H2O + 2e 3OH +0.88
+ –
O2 + 4H + 4e 2H2O +1.23
– –
O2 + 2H2O + 4e 4OH +0.40
+ –
O2 + 2H + 2e H2O2 +0.68
– – –
O2 + H2O + 2e HO2 + OH –0.08
2+ –
Pb + 2e Pb –0.13
4+ – 2+
Pb + 2e Pb +1.69
+ – 2+
PbO2 + 4H + 2e Pb + 2H2O +1.47
2– + –
SO4 + 4H + 2e SO2 + 2H2O +0.17
2– – 2–
S2O8 + 2e 2SO4 +2.01
2– – 2–
S4O6 + 2e 2S2O3 +0.09
2+ –
Sn + 2e Sn –0.14
4+ – 2+
Sn + 2e Sn +0.15
2+ –
V + 2e V –1.20
3+ – 2+
V + e V –0.26
2+ + – 3+
VO + 2H + e V + H2O +0.34
+ + – 2+
VO2 + 2H + e VO + H2O +1.00
– + – 2+
VO3 + 4H + e VO + 2H2O +1.00
2+ –
Zn + 2e Zn –0.76

All ionic states refer to aqueous ions but other state symbols have been omitted.

8
Cambridge Pre-U Revised Syllabus

(b) E in decreasing order of oxidising power

(a selection only – see also the extended alphabetical list on the previous pages)

Electrode reaction E /V

– –
F2 + 2e 2F +2.87
2– – 2–
S2O8 + 2e 2SO4 +2.01
+ –
H2O2 + 2H + 2e 2H2O +1.77
– + – 2+
MnO4 + 8H + 5e Mn + 4H2O +1.52
+ – 2+
PbO2 + 4H + 2e Pb + 2H2O +1.47
– –
Cl2 + 2e 2Cl +1.36
2– + – 3+
Cr2O7 + 14H + 6e 2Cr + 7H2O +1.33
+ –
O2 + 4H + 4e 2H2O +1.23
– –
Br2 + 2e 2Br +1.07
– – – –
ClO + H2O + 2e Cl + 2OH +0.89
– + – +
NO3 + 10H + 8e NH4 + 3H2O +0.87
– + –
NO3 + 2H + e NO2 + H2O +0.81
+ –
Ag + e Ag +0.80
3+ – 2+
Fe + e Fe +0.77
– –
I2 + 2e 2I +0.54
– –
O2 + 2H2O + 4e 4OH +0.40
2+ –
Cu + 2e Cu +0.34
2– + –
SO4 + 4H + 2e SO2 + 2H2O +0.17
4+ – 2+
Sn + 2e Sn +0.15
2– – 2–
S4O6 + 2e 2S2O3 +0.09
+ –
2H + 2e H2 0.00
2+ –
Pb + 2e Pb –0.13
2+ –
Sn + 2e Sn –0.14
2+ –
Fe + 2e Fe –0.44
2+ –
Zn + 2e Zn –0.76
– –
2H2O + 2e H2 + 2OH –0.83
2+ –
V + 2e V –1.20
2+ –
Mg + 2e Mg –2.38
2+ –
Ca + 2e Ca –2.87
+ –
K + e K –2.92

9
 Electrochemistry
⑦. Fells solution is brushed on the
copper printed circuit
board a pale blue solution is produced. Calculate cell
write redox
3
equation.
Fes+3e:· Fe.0.0nX
Feb +Co pale blue solution
Fe3++ e- -· Fest 0.77X +

Ee1 0.77-0.34
=

=
0.43 iron in
agrees form
=

Cv" + 2e 20 +

0.34
.

Fe3T+ e · Fesx2
-

(r. -
cu + 2e CFeS+CO [Feet Cutpale blueofthe

Test of Cations:
agNaOH
Fet+IOHy
lagi
·
FeOHcis Precipitation
air, Redox
FeOH,,, FeOHsis
Fe
·
"agi
tle- FeOH, tOH-0.56X
FeOH,,
·

+ -

Conditions 02 4H 4e 2H0
Acidified
-
+
+

Alkaline Conditions" OctzH0the--40H +0.401

Acidified Hc0c Oc 'Oc+CH++2e -

-

HO
"

Hc0 Alkaline OctHOtZeT HOitOH-

(Sep 0.40 0.46

-

= --

0.56 =
n*FeOH, +1e -
-

FeOH, +OH-
-

0+ 2H20 + 4e -
-
40H-

4Fe OH, stOc +2H20 '4FeOH, rust

 +
+
Electrochemistry
Q. (v' 13 , ? +

+ +
v- H,0. 10+2H e 0.34
-

-
+ +
+

(v*+2e= 20 + 0.34
7

reduced

Cr+2X*+ 2Hc0 <

2X0, 4H CO +
+

focell 0.34 0.34 Eee1 O Not

feasible
= -

9. turn brown to air, what is the

Ifredox
apples on
exposure
equation of a
peeled apple turning brown?
Calculate cell.
+ -

0 4H
+
+ 4e -

2H20 + 1.23X
-

Fest+ e -
-
Feet + 0.77X

4Fe"+40c + 16H+ > 4Fe3+ 8HcO

+

Eel: 1.23-0.77 =
0.46

Interesting.
used KMno, notdilute
Why dilute H.SO, is to
acidity
HCl? dil. H.SO, -dil. HCl

KMnOu KMnOn
+1.52X MnOn'+OH+SeT, Mn+hHcO
+2.0lX ScOo+Ze-, 2SOn

Exe1:1.52-2.01 sOn" does notreact.

not
feasible thus
 Electrochemistry
MnOn'-OH +5eT, Mn" +4Hc0
+1.52X
-
EOcell =
1.52 -

1.36
H.361(l + 2e-, ect
feasible
Since HC reacts, H.SOn is
:

preferred.
He does not reactwith
HeSOn because I is
too small.

Hbr 5 HcSOn Eell comes out

negative. Butusing
concentrated H. SOn makes feelpositive a reaction
becomes
feasible.
 Electrochemistry
Lead-Acid Car Battery:
Process
Charging
Electrolytic cell

Discharging Process
Electrochemical cell

12X 2/ M/ HcSOn
V

Pb-- ph" + 2e
-

-0.13
+
1
V

pb0c + 4H +2e-- ph" + 2H,0 + 1.47

A V

Anode Cathode Pb0c + Pb + 4H + -2ph" + 2H,0

pb PbOc
p+
HN0z Eeey=1.601 if we
replace HNO, with
M/ HaSOu HeSOn, 4H-2 ph" as
-

=0 t02X PbsOn forms. Equilibrium

shifts forward a feel
Lead Acid
Advantage of Battery Cheap

Disadvantages: Notenvironmentally friendly

Non portable
Provides non constant
voltage
 O
Electrochemistry
E & Oxidising/Reducing Power:
Group 1
Ipanomaly to decreases
2.71 Nattel Na-2.71 metal increases
+

2.42
+

k
"

+ e. .
-
1 -

2.92
Reactivity of
Rb down the
group
CS
If anomaly -
E0c1 Reactivity of metal

Group 17
Ftee: ·
2F +2.071 to decreases
cletee: cel +1.361 metals
Reactivity of non -

Britce: CBr ·
+1.071
lette: ·2F +0.544 down the
group
v

①. Cl. + sn <0. excess (l+S p <

Redox+Eell? Redox+Ecell?

(l 2e +

(C +1.36
snsnize- -

0.14 In excess, Cle may react with

Spt
-

<Pep 1.36 = + 0.14 (l 2e+

(C +1.36
1.50
=

snsnize- -

0.14
(l sn,2Cl + s
+

(l 5n,2Cl sn't
+
+
E0 = 1.50
-

Add 122. (l 2e+

(C-
+
Sp+, sn"
-

2022 5n,Sn"+ hcl

+ + 2e
>s+Cl sn"+ + 2Cl-
[0: 1.50 + 1.21 =
1.71
20 1.21X
=
 Electrochemistry
①. Fe3+ X.?+

excess

selectthe
equation for
excess reactant that
results in maximum
oxidation
continuity
other reactant.
or
of
 Electrochemistry
Homogenous Catalysis:
Redox
Fest
500" +

2I ·250g + Ic +201S,0"+ 2e= 250, -

lagi cagi lagi lagi 21

+0.541,
-
+ 2e -

Felt + Fe*+ 0.77X

.

(Sep +
=

1.47X e. .
.

In the
Homogenous catalysis, charge on
catalyst
lie in beterone
mustbe
most
oppositeatotaleofcatalyst
Fe + Fe
.

e. .
.

-
S,0+ 2e= -2s0,-
21 · 1 + 2e Fee- -
F*"+ e-
+ + "+
2Fes + 2 1 , 2Fe' + Ic S,O+2Fe'+, 2SOn zFe
50cell =
0.77-0.54 EOcell =
2.01 -

0.77
0.23X
=

1.24X
=

2FesTACT. efect,
the +0.23
 Electrochemistry
①. Mn + ph2+, G8 =-

nFETel, 96500Cmol"
no.
of moves of e-in
balanced
equation

f 80+0.059109,
=

he
 Electrochemistry
PuriÞcation of Copper:
+
-

Anode Co Cu"+2e <

Cathode Cv"+2e Cu >

-
0.80

Con Pure Cu
Anode
+ 0.76
Age: Ag +0.801
0.761
>

Cathode zn+ 2e
zn
+ -

[ +

10.34CU+Ce= CU +0.34X
& impurities
sludge CUSOniql
Impure Cu
Anode Zinc oxidizes as it has a positive e.m.)
or oxidation potential.

Thus, the in anodic

main
impurity sludge is Ag as

itdoesnotoxidize.Holeverifa halequationhasbeen
oxidation will occur. Thus, co oxidizes.

Cathode
0.761 Co reduces it has
zn+ 2ezn Only as
-
+ -

positive E?
=

(v"+(e ·
Cu + 0.34X a more
+
2H + e7 ·
He 0.004
 2

Answer all the questions in the spaces provided.

1 An electrochemical cell is constructed using two half-cells.

● a Br2/Br – half-cell
● an Mn3+/Mn2+ half-cell

(a) State the material used for the electrode in each half-cell.
platinum
Br2/Br – half-cell ..........................................................................................................................
platinum
Mn3+/Mn2+ half-cell .....................................................................................................................
[1]

(b) The cell is operated at 298 K.

The Br2/Br – half-cell has standard concentrations.

The Mn3+/Mn2+ half-cell has [Mn3+] = 0.500 mol dm–3 and [Mn2+] = 0.100 mol dm–3.

(i) Use the Nernst equation to calculate the electrode potential, E, of the Mn3+/Mn2+ half-cell
under these conditions.

20
E
0.05Plog (0X.]
= +

[red]
1.44 +1.53 V [2]
0.0591090.
+
=

E = ..............................

(ii) Calculate the Ecell under these conditions.

Mn*+ e- . Mn++1.53 1.53-1.07

BV+Ce= 2Br + 1.07

+ 0.46
Ecell = .............................. V [1]

(iii) Write an equation for the overall cell reaction that occurs.
+
Nn3 e
-

2 x +
Mn+
-

2Br ,Brc + 3e

2Nn** + 2Br, 2Nn* + Br,

....................................................................................................................................... [2]

© UCLES 2019 9701/42/O/N/19

 3

(c) An aqueous solution of copper(II) sulfate is electrolysed using copper electrodes. A current of
1.50 A is passed for 3.00 hours. 5.09 g of copper is deposited on the cathode.

The charge on one electron is –1.60 × 10–19 C.

The relative atomic mass of copper is 63.5.

Use these data to calculate an experimentally determined value for the Avogadro constant, L.
Give your answer to threeVLJQL¿FDQW¿JXUHV

0 1 1.5= =
x 3 x60 x60 =
16200C

CU 5.04 0.00 1 mol.e-

n
X:charge on
=
=

63.5
=>
101051.08
+ -

(v' + 2e , Cu
: 1 101051.08: 6.32
=

103
x

-19
0.08:16200 1.6 x10

1 =

6.32 +
183
L = .............................. mol–1 [5]
x 202102.16
=

(d) Explain why magnesium metal cannot be obtained by the electrolysis of dilute aqueous
magnesium sulfate. Your answer should include data from the Data Booklet.
-+
2e= 2.384
Mq Mg
-

....................................................................................................................................................
2H +2e. · He
+

0.00X
....................................................................................................................................................

....................................................................................................................................................

Preferential discharge of Hc.

.............................................................................................................................................. [2]

[Total: 13]

© UCLES 2019 9701/42/O/N/19 [Turn over

 Electrochemistry
⑦. >
-
>
-
Exep:1.50Y
e e

Bridge
Salt

Metal M Zinc
ive electrode +ive electrode

M(x* +
xe-
Imol. dm' N+* Imol.dm's In

Find 10 NM*. 1.50=.0.76 -10 0 =

2.26

9. When CmAcurrent for 2 days through M*q

flowed
that
solution, it was
found 0.071g of metal N
the cathode. Calculate oxidation
were

deposited at
of
metal M. Arm: 60

Q:H (2 103) =

+
2 24
x + +
60x60: 345.6C

M= 1.14 x103
n
0.0716.
1.14 x 10-3:3.58"10'
" -

+
x xe - M 1:3

1 mol. e. 96500 :**ANS.

xmol. e -:345.6

X 3.58
=

103
+
 Transition Metals
transition metal
Every
is and block metal,
but all a block metals
are nottransition.

Non transition elements

FirstTr a n s i t i o nseries
max 0X.
de-
scandium so
#
of Unpaired
1
state
152s'2p353p3d'4s + 3

2 + 4
+5
3
5 +6

+7

s +6

+5

2 +4

0 anomaly +2
Zinc In 152s'2p353p'd 43 0 +2

Due to close
proximity of energy of 4s to3d, electrons
-

can be lost
from either level leading variable oxidation
states.

Maximum Oxidation state 3dec+4se-

of unpaired
Transition Metal:
at least stable ion with
It
forms partially filled
-

one

d orbitals.
 Transition Metals
zinc a scandium
form ions with
completely filled
d orbitals or nod orbitals. Their other ions are

unstable.

So Ti 1Cr Mr FeCO Ni Cu En

H
+2 +
2 2
+ +
2 +
2 2
+

+2 +2 +2
+3 +3 +3 3
+ +

3 +

3 +3 +3 +3

+4 +4 +4 +4 +4 +4 +4

+5 +5 +5 +5 +5

+6 +6 +6 Most stable
+7

convention based oxidation state

Naming on

Higher
-

ions exist
oxidation states
either
of metal Copper 11
sulfate, COSOn
as oxonium
Manganese IV Oxide, MnOc
or
complexes. e.g.
7
Mn+ >
MnOn- + 62-
Tr a n s i t i o nmetal ions exist as
+ 62 -

+5
Cr >
CrO7 or CrOn colored compounds.
 Transition Metals
Physical & Chemical Properties:
A metallic
bonding
physical PI.
They have high melting points. Strong in transition series:
C chemical
atomic radius remains constant
3d
charge shielding effect "as filled
02. have
high density,
nuclear
They ionisation
energy remains
fairly constant

hard construction material

Ps.
They are
rigid useful
good conductors heat
Ph.
They are
of electricity.
Cs. have variable oxidation states.
They
C 6.
They form complexions.
Tr a n s i t i o nmetals their compounds act
27. as
catalysts.
18.
They form colored compounds.
Comparison of s-block & Transition Metals:
Ca with Tr a n s i t i o nMetals'
·

840 Ti 1660
=

Ca is lower than that

1.
m.p. of of a transition metal.

a is lower than that transition metal.

2.
density of of a

atomic radius Ca is than that transition

3.

metal.
of larger of a

ionic radius catis than that

2.

metal.
of larger of a transition
 Transition Metals
Ca is lower that transition
5.
first ionization
of of a

metal.

than that
6. electrical
conductivity of
transition metal
(a is
higher of
a
exceptCo.

Redox Titrations:
Felt acidified KMnOu Color at start colorless
indicator color atendpointpale
no
pink
KNInOn known cone.

dil. HSO, MnOn+SH+5e= Mn + 4Hc0

excess -

Fe'known vol. 25cm' 5 Fe* · Fe++ e-

x

lag)
conc.?
MnOntOHSFet, Mn"+5Fe*+4HcO
nMnOn inFetin2scm> Fel
i. iii.conc.
of
Practical
Activity Iron tablet
0.420
of dissolved excessacid t h at
so

all of
the ironare on are cag
solution obtained was titrated against 0.04 moldm' KMnOn.
The titration obtained was titrated 0.04 mol dm'
against
KMnOn. The titre volume was 23.50cm.
n 2 x1
=
=
0.04 x 23.5 = 9.4 +10"mol.
1000
Calculate number MnOn-in title
a ·

of moles of Fet in the solution

n 9.4 10
=
+

4.7 x 10-3
=
-
x5

b.Calculate number
ofFeltmoles of
in the solution. Ar 55.8
mass:4.7 x

55.8
10" x

2.Calculate mass
of =

0.2689
d. Calculate: iron in iron
mass
of 0.420g of ore. 1. =
0.2621100
0.420
 Transition Metals
Redox Titration
Example of
-

2(v"+ 2e - zcut
excess Ijagu 21 <1 + 2
-

2CV' + 2I< 2Cu+ Is

CUSOniag
ag.blue solution 2CV' + 4I <2CUT 19)+1215)
-
-

White brown
ppt.
~conc.?

We will titrate the mixture with known concentration

MacScOs
of .

n NacS,Oz CxY =

known cone. Volumetitre 1c +

25c05,21+Sc0
starch indicator NarScOs ·
n I, in the mixture
Is ·

n Cut in the mixture

cust
·

cone,
of
starch NazS,Os
mustard brown, blue black
yellow ·colorless

Redox Titration
Example of
-

COn ,2CO, +2eT

Autocatalyst 9

MnOBH+5e- Nn"+8HcO
SCOs +2MnOs +I6H" l0COs +2Nn' OHcO

This reaction is an
example of autocatalysis.
known conc.
of KMnOu Color atStartcolorless
dil. HSO,
Endpoint Color Pale Pink
COniag 25cm3
 Transition Metals
Complex: >cation anion
-

It is a molecule or an ion with central metal ion

covalently bonded to ligands.

dative

Geometry of Complexes:
Linear Complex Planar Te t r a h e d r acomplex
l
Square
complex
4
2 H

complex 6
Octahedral

written above
Coordination Number:
Itis the number dative bonds
-

of formed by ligands
with a transition metal ion in complexes.

Ligand:
Itisa moleculeoran anionwithalonepart the
-

of

complex.
 Transition Metals
Types of Ligands:
it dative bond with
Monodentate
ligands
in
forms one

transition metal ion a complex e.g. H.0:, MHs,

R OH, R MH, Ct, OHT:CN, CHg c o, etc.
⑥

Bidentate that forms two dative

covalent
Ligands
bonds with
a
ligand
transition metal ion in
1.
a
..
complexes
e.g. H8 CHICH OH, OH CC0 diamines
OH,..
00

Hexadentate that sixdative

ligands a
ligand forms
covalent bonds with
a transition metal ion in a
complex
ethandiamine tetra
EDTA acetate, ethanoate
e.g.

Naming Convention
Shapes of Complexes:
MHz amine

Hi0 agra Linear Complex MLz

OH hydroxo
monodentate
2 Chloro
* ligands are
Br Bromo
\L <M*1] name
of ligand followed by metal
I To d o

CN-
Cyano
e.g. (AgNHsc" diamine silver I
Transition Metals
Te t r a h e d r aComplex.
l ML
-

ICOC1] *
Te t r a c h l o r o c o11
balt .N I

have to be monodentate
Ligands
-

(CuCl4)*
Te t ra c h l o ro c o p p11e r
Planar complex. M1
Square
↓ ↳mono (NiCN, 1"
L
I L

2bi
e.g.
N N 11
-r 7 f Tetracyanonickel
1 bi2mono

(PtNHzcCre]
diamine dichlore platinum 11

identate
2
ligands square planar key ·diethanoate

IFe CcOnd] diethanoate iron 11

oo
2
-

Fe
oo
oc C 0 0 0
Fe
oc c0
00 Fe
Transition Metals
1bidentate 2 monodentate
square planar +2

" HcN OH
ICO HeNCHeCHeNHa HO, CHz
CO
CHz
HaN OHz

Octahedral complexes M16

6 mono 3bi Zbicmono 1bi Mmono Ihexa
+

(Fe H,0,3
Hexa iron III
aqua

3 bidentate
ligands "

ICO HeNCHzCHzNHc,]
Ethan 1,2 diamine cobalt

I so
"chelate shape

with 4 monodentate In order to

ML
-

ligands.
will
differentiate
between
square planar
or tetrahedral, we
employ
Stereoisomerism.
 Transition Metals
Superpoints: for stereoisomerism

1. Tr a n s i t i o nmetal ions exist as

aquations.
C"
27lag
ICUHO, water will
always be 6 in complex a

Fe IFe Hc0s]" will

aqua complex always
be octahedral
lag

ICU H0,/SO4
CUSOnag cagi
hexacoppersulphate

How metal ion

2.
many ligands a can
form?
Dative Bonds=oxidation state metalion 1
#of of a

Which
3. complexes exist or not?
-
Salt sheet'
Analysis OH NHg + HcO--NHy +OH
Te s t Cations NaOH
in case
of ag. ag. NH,
of 2
NaOH, ppt. En+ white ppt. white ppt.
a complex soluble in excess soluble in excess

are caused

by OH Cut blue ppt. blue ppt.

insoluble in excess soluble in excess

in
deep blue sol
ag. NH,,
OH
forms
ppt. 5, NHs Felt green ppt. green ppt.
forms complex insoluble in excess insoluble in excess

Jission la dissolve kar

-

ppt. excess
reagentmein
ion ke saath complexban one
reagentne
jaye.wahan
Transition Metals
Q. State oxidation state
Will NH3 displace
OH ions when
the
of the T. M in each

they make the

complex.
soluble solution? 0

Ye s . ICONHsINCNs ICON
2
+

All complexes are CuOH: H20;

soluble in water?
Yes. Also
give the formula of complexformed a

bu NiS EDTA

IN EDTA "J"

Reversible Ligand Exchange Reactions: conc. HCl

conc. Nach

few drops NAs followed by excess of NHzcagi

of CONC. Cl

Cy2 - - -

Co - - -

Ni2t - - -

ag NHs -

Aqueous NH, NH, +HcO-NH+OH

..?⑧
ag. [USOn Precipitation 2t
w/
few drops also considered ligand exchange
ICUH0s]+2OH's ICuOH, H0n1+2H20
few drops of ISI

NHs ICU HOs+2OH' CrOH, 6H,0

both correct.
equations are
Transition Metals
Excess
of ag. NH, exchange reaction always
ligand deep blue

CuOH, +6NHs -ICU NHs.cl + COH-

NHS in excess

CuOH, HO, +6NHs-ICU NHscl+ COH'+4H,0

deep blue
CU H2O,SOn CU MH, SOn
NHs pale blue blue
ag 2t deep
W

·
(CUH00l 6NHs- + ·
ICU NHs ol+6H,0
.
ICUHO. +4NHs--ICUNH, a HO,Y4H,0
ag. [USOn

Reaction with conc. CI

~CONC.
Cl ICUH0.+4C---(uCla)"+GH2O
pale blue yellow
at
.
ag. [USOn
blue
green equilibrium
pale
molecular
formula
CUHcO, SO4 +4HCl-HcCuCly+6HcO+H,SOn

[02
-

Aqueous NH,

IC0 HOs+COH- .

COOH, HOn+2HO Precipitation

or LER
blue
pink solution ppt.

COOH, HOn+bNHy-ICONHsYCOH' 4H2O LeR

Transition Metals
->
cona. Cl

120 H.0s! +4C--.(CoClal+GH,0 veR

solution blue solution

pink

Ni2t
-

Aqueous NH,
(NiHOs) +COH- .

NiOH, HOn+2HO Precipitation

or LER
solution
green grey green ppt.

NiOHc HOn+bNHy-INiNHssYCOH' 4HEO LeR

blue solution
grey green ppt.
->
cona. Cl

(NiH0s+4C--. (NiCll"+GH,O veR

green
sol.
yellow solution
Transition Metals
Color of Complexes:
1. Basic Conceptof Colors

2. Shapes of d orbitals

colored?
3.
Why complexes are

Basic Concept of Colors:

Color observed is to the color
-

complimentary
absorbed.
E
hf
=

I X
I am
increases
intensity ofred intensity blue increases
of

>
400nm 700nm
A increases

A decreases
I decreases

More intense the color

-

absorbed, more intense

the color observed.

Absorbance Color
red blue
red
blue red green
Transition Metals
Shapes of d-Orbitals:

in by the the
axes
along axes

Color of Complexes:
E
hf
=

How metalion?
-

ligands approach a

metal ion in two

·
ligand approach
can
ways
i. in by the axes
dx,dy,dz
ii. the dz"
along axes
dxy's
-
Nature
of ligand also affects the color
of complex

Strengthof ligand (CuNHs]"ICuClal"

deep blue yellow

On approach of ligands
d orbitals splitand

become non
degenerate
Transition Metals
In between the Axes ML4 Te t r a h e d r a l

E
Generally z
hf=

for ML6 f is frequency of

complexes is
excitation
ofe, visible
light
than
greater Blue Light smaller t

for ML4
I ·

·
larger
smaller 1
i absorbed

emitted

the Axes ML6 Octahedral

Along
Light
YIBGYOR, I

L
·
Greater t
smaller i absorbed
x increases
excitation of
e
·

larger is emitted

smaller it is absorbed
it
as
gains greater energy
due to
Red greater frequency
I energy gap t is larger

metal ion either in between

Ligand approaches
-
a

On the
along the
or axes. approach of ligands,
d orbitals splitdue to electronic
degenerate
repulsion.
e in the low
-

energy d orbital
gains energy from
lights excite to
higher energy d orbital. The color
of the complex is complimentary to color absorbed.
Transition Metals
-
Nature
of ligand affects the splitting of d orbitals
I therefore the is also affected. Since
energy gap
frequency oflightabsorbed will change, thus the
color
of the complex changes accordingly.
M4 complexes blue in color, butif
-
are
usually
reddish itmeans thatthe
they are
energy gap
is more than normal. (CuCln)" yellow
red in color but
ML6 complexes are
usually if
they are bluish, itmeans thatthe energy gap

thannormal.It
esser
costinght emittee
~? ·as
completely
d orbitals
filled
-light
No orbital
for excited
e-
d orbitals.
zinc ion also has
completely filled
-

Scandium's block metal ions do not have

d orbitals. Thus no color.
 Transition Metals
Absorbance Spectrum: 400nm 700nm
red
violet
color observed is Absorbance
Blue M14,
to energy gap
complimentary

↑
the color absorbed between splitted
d orbitals is lesser

Red M16,
energy gap
between splitted
507 P4 04 now 500 boo too good orbitals is
greater
visible spectrum Anm
~09 P4 &3
Absorbance Absorbance in blue
red
regions thus, green
color

Green colored compounds

are tetrahedral a
square
in
now soo goo too woo 'planar shape
Anm
 Transition Metals
Stereoisomerism of Complexes:
Geometrical/somerism Optical/somerism
ML4 complex
If an
Planar Complex Te t r a h e d r aComplex
l
shows is, trans
1.
Square 1.

1MX,Y) where X 3 Y are (MABCD) all are mono

isomerism, itis
monodentate dentate All 4
ligands ligands.
confirm square IY HO, MHsc
2 t

bonded to metal
planar, as tetrahedral
e.g. ligands
does notshow 2. Octahedral Complex
ion are
different.
geo
isomerism. IMXY)X a Y are mono c. Octahedral Complex
dentate
ligands IMAs] A bidentate
=

IMA,B,] A bidentate
=

(MAcBc) A bidentate
=

B monodentate
=

B monodentate
=

Arrangementof BY will (MX)XaY are mono

define is, trans arrangementdentate ligands

Geometrical Isomerism:
cis, platin binds to Square Planar Complex
1.

the
segment of MXY PFNHscClc-Cis, platin is more

anti
DNA stops the
polar. Used an

replication process cancer

drug.
cells.
of cancer

which show isomerism in

ThoseM14 complexes geometrical are
square planar shape
I nottetrahedral.
Transition Metals
2. Octahedral Complex
IMXaY) X=monodentate
e.g.
Y=monodentate (CONHs, HO,7

IMAcBc] A:bidentate e.g.

B monodentate
=

(NiHNCH.CHNHcc H2O 2
7"
(NiHNCHCHzNHccClc]
Transition Metals
Optical Isomerism:
1. Te t r a h e d r aComplex
l

IMABCD1 all ligands are

differenta monodentate.

e.g. (NiHOCl CN MH,]

H20 H20

Ni Ni
ce*1 HHs HgH 1 *C
CN CN

ML4 be tetrahedral
can
square planar s or I.

-
Yo u will have to memorize shapes for some.

ICUCla)" T ICUCl H20c] S ICO en HcOc7 S

shows stereoisomerism ethandiamine
ICOCl)" T
(NiNH, Cl) T Koen S
(NiCla]" T Does notshow stereo
isomerism

2. Octahedral Complex
M

monodentate
IMX) X a Y
2
are
ligands.
L 2
NHs NHs
H20 NHs HIN OHe shows cis, trans.
IMXaY) Only
CO CO
cis isomer shows optical isomer
HCO OHz H20 OHe
HO H.O

For M14 complexes, shapes need to remembered.

some be
If an M14 complex
shows stereoisomerism, itis square planar. If it does notshow stereoisomerism,
itis tetrahedral. Remember, in tetrahedral complex, all monodentate,
a
ligands are

the
otherwise, shape is
square planar.
 Transition Metals shows is, trans
(MAcBc) A bidentate
=

e.g. E is shows optical

B monodentate
=

(NiHNCHCH2NHzzCl2]

Cl2 Cl 2 Cl2
Cl2
Ni Ni
>
W

IMAs] A bidentate
=

Main isomerism
shown
by (MAcBc
Iien,
a (MXaY] are is,
trans. Unless asked,
do nottell that is
shows optical.
 Transition Metals
Stability Constant: Kstab

ICUH0.+4C---(uCla)"+GH2O
Water is notwritten
in the stab

expression - Ksiab=(/CuCla)"] · 3.48 "0" mol"dm"

IICUHOs!" (e-"
Kstab 5.6
log
=

ICUHO. +4NHs--ICUNH, a HO,Y4H,0

Reaction stepby steps NHs

-

occurs a single
replaces a
single H,0, until product.

Kstab K, K,*
=

Ks* Kn

Kstab tells us:

1.
Stability of complex
Reaction
2.
of ligand
a

3.
Strength of Dative Bond
Transition Metals
Example Ligand log stab
Cl 5.6
NHs
I w

NaCl Cl-
NHs 13. 1

· ICUHOs?"color of solution turns deep

paleblue
blue ba NAs prevents Cl

HCR NH3 from attacking.

~ W

NHs+H*s NH4 NAs is exhausted by HCl.

· (CU H20 ol
color turns
pale blue yellow.
(NH,) (HC1]
=

HCR NH3

~ W

2t
color
of solution turns
deep
· (CuH0l blue.
pale blue

(NH,) (HCl]
HCR NH3

His is exhausted
~ W

HCl.
by
· ICUHOs?"color turns
yellow.
pale blue

(NH,) (HCl]
Transition Metals
Stability Constant Correlations:
Ligand log Kstab
NH3 6.5

HN CHcCHc NH, en 21.0

Hc0 4.0

OH

25.0

OH

ICU Hc0.+GNHs ↳
·
ICU NH3 a HOc]4H,0
5 5

ICuHO,?tedta". ICu edta *6H,0

2 + S 7

If a more
polydentate ligand is used, the entropy
change will be much more positive. And, the
complex formed will be more stable.