Kimia Dasar

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ATOMS, MOLECULES AND MOLES

- In ancient time, people believe in phlogiston theory


- Antoine Lavoisier (around the end of 18th century)
experiment’s comes into the conclusion of conservation
of mass law:
In any chemical reaction, mass is neither
created nor destroyed
- Joseph Proust (around the end of 18th century)
experiment’s results law of definite proportions
(composition):
In any sample of a pure chemical substance, it
always finds the same elements in the same
definite proportions by mass

- Postulates of the atomic theory (John Dalton,


beginning of 19th century):
1. Matter is composed of tiny indivisible particles called
atoms.
2. All atoms of given elements are identical, but differ
from atoms of other elements.
3. A chemical compound is composed of the atoms of
its element in a definite fixed numerical ratio.
4. A chemical reaction merely consists of a reshuffling
of atoms from one set of combinations to another.
The individual atoms themselves, however, remain
intact and do not change.

1
Let’s see molecule AB where an atom of A is twice as
heavy as an atom B

Number of Number Mass of Number Mass of Mass Ratio


Molecule of Atoms A of Atoms B (Mass A)/
of A of B (Mass B)
1 1 2 units 1 1 units 2/1
2 2 4 units 2 2 units 4/2 = 2/1
10 10 20 10 10 20/10 =
units units 2/1
500 500 1000 500 500 1000/500
units units = 2/1

By product of Dalton’s atomic theory: The multiple


proportions:
If the masses of one element are the same in the two
samples, then the masses of the other element are in ratio
of small whole numbers

Example: For CO and CO2; ratio of O in CO / O in CO2 is ½

The Mole Concept


1 atom C + 1 atom O  1 molecule CO
100 atoms C + 100 atoms O  100 molecules CO
6.02x1023 atoms C + 6.02x1023 atoms O  6.02x1023 molecules CO
1 mole atoms C + 1 mole atoms O  1 mole molecules CO

1 C + 1 O  1 CO
C + O  CO
2
Atomic Mass:
Carbon-12 is assigned as exactly 12 u (units)
1 mole Carbon-12 = 12.0000 g
1 mole C (mixture of C-12 and C-13 in nature) = 12.011 g

- Percentage Composition
- Molecular Formula and Molecular Structure
- Relative Molecular Mass and Molecular Mass

3
CHEMICAL REACTIONS AND THE MOLE
CONCEPT

Chemical Reaction:
H2 + O2  H2O

C + O2  CO2

Na2CO3 + HCl  NaCl + H2O + CO2

Pb + HC2H3O2 + O2  Pb(OH)C2H3O2

Pb(OH)C2H3O2 + CO2  Pb3(OH)2(CO3)2 + H2O + Pb(C2H3O2)2

Balancing Chemical Equations


Step 1. Write an unbalanced equation, being careful to
write the correct formula for each substance
involved.
Step 2. Balance the equation by adjusting the coefficients
that precede the formulas of the reactants and
products so that there is the same number of atoms
of each kind on both sides of the arrow.

Example:
Na2CO3 + HCl  NaCl + H2O + CO2

Na2CO3 + HCl  2NaCl + H2O + CO2

Na2CO3 + 2HCl  2NaCl + H2O + CO2


4
Is it correct to write the reaction in the following way?
5Na2CO3 + 10HCl  10NaCl + 5H2O + 5CO2

Exercise
C8H18 + O2  CO2 + H2O

Calculations Based on Chemical Equations


The combustion of ethanol:

C2H5OH + 3O2  2CO2 + 3H2O

1 molecule C2H5OH + 3 molecules O2 


2 molecules CO2 + 3 molecules H2O
1 x 6.02x1023 molecules C2H5OH + 3 x 6.02x1023 molecules O2 
2 x 6.02x1023 molecules CO2 + 3 x 6.02x1023 molecules H2O

1 mol C2H5OH + 3 mol O2  2 mol CO2 + 3 mol H2O

The coefficients in a chemical equation provide the ratios


by which moles of one substance react with or form
moles of another

Problem: How many moles of oxygen are needed to burn


1.80 mol C2H5OH.

5
Calculation Involving Grams
How many grams of oxygen are required to react with
0.300 mol Al and how many grams of Al2O3 will be
produced in the reaction: Al + O2  Al2O3

Limiting-Reactant Calculations

In an experiment, 12.0 g of Zn is mixed with 6.50 g of S


and allowed to react. Which is the limiting reactant?

Theoretical Yield and Percentage Yield

actual yield
Percentage yield =  x 100 %
theoretical yield

Ethylene, C2H4, is burned in air to form CO2 and water


according to the equation C2H4 + O2  CO2 + H2O.
When 1.40 g ethylene is burned and gives 1.44 g of water,
what is the percentage yield of water?

6
Reactions in Solution
H2 + O2  H2O
C + O2  CO2
Na2CO3 + HCl  NaCl + H2O + CO2
Pb + HC2H3O2 + O2  Pb(OH)C2H3O2
In what phase are the reactants?

NaCl(aq) + AgNO3(aq)  AgCl(s) + NaNO3(aq)

(aq) to show that the compounds are in an aqueous solution


(s) to show that the compounds are in an solid phase (precipitate)
(g) to show that the compounds are in an gas phase
(l)
Terminology applied to solution

Solute
Solvent
Concentration: molar (M), molal (m), mole fraction (x),
% (w/w), % (w/v), %(v/v)
Concentrated
Dilute
Mole(s) of solute
molarity (M) = 
liter of solution

mole(s) of solute
molality (m) = 

kilogram of solvent

7
Calculating the molarity of solution
A 2.00 g sample of sodium hydroxide, NaOH was
dissolved in water to give a solution with a volume of
exactly 200 mL. What is the molarity of this solution?

mass of an element
number of moles (n) = 

relative atomic mass

mass of a compound
number of moles (n) = 

relative molecular mass

How many milliliters of 0.250 M NaOH solution are


needed to provide 0.020 mol of NaOH?

How many grams of NaOH are needed to prepare 500 mL


of a 0.300 M solution?

Preparing solution by dilution

Reagent Density Percent by Molarity


(g/mL) mass
Sulfuric acid, H2SO4 1.84 96 18
Hydrochloric acid, HCl 1.18 36 12
Phosphoric acid, H3PO4 1.70 85 15
Nitric acid, HNO3 1.42 70 16
Acetic acid, HC2H3O2 1.05 100 17.5
Aqueous ammonia, NH3 0.90 28 15

8
M.V = (mol/L) x L = mol

M1.V1 = M2.V2

How many milliliters of concentrated sulfuric acid are


required to prepare 750 mL of 3.00 M H2SO4 solution?

The stoichiometry of reactions in solution

Aluminium hydroxide, Al(OH)3, one of the antracid


ingredients in Maalox, can be prepared by the reaction of
aluminium sulfate, Al2(SO4)3, and sodium hydroxide,
NaOH. The balanced equation for the reaction is
Al2(SO4)3(aq) + 6NaOH(aq) 2Al(OH)3(s) + 3Na2SO4(aq)
How many milliliters of 0.200 M NaOH solution are
needed to completely react with 3.50 g Al2(SO4)3?

Limiting reactant in solution reaction

How many grams of solid AgBr will be formed if 50.0 mL


of 0.180 M AgNO3 are mixed with 60.0 mL of 0.850 M
CaBr2, where the balanced equation is
2AgNO3(aq) + CaBr2(aq)  2AgBr(s) + Ca(NO3)2(aq)

9
THE PERIODIC TABLE AND SOME PROPERTIES OF THE
ELEMENTS

Some properties of the elements

At room temperature: gas, liquid, solid


metallic, non-metallic
soft, hard
very dense, low density

Is it possible to classify the elements, so they can be easily


studied?

The simplest method: divide into three categories


1. Metals: iron, aluminum, copper
have a high electrical conductivity
2. Nonmetals: carbon, helium
very bad conductor
3. Metalloids: silicon, arsenic, antimony
semiconductor

Dmitri Mendeleev (early of 1869) and Julius Lothar Meyer


(the end of 1869) arranged the elements in order of
increasing atomic mass; they found that the elements with
similar properties occurred at periodic interval.
They have made the first periodic table.

10
11
The modern view of the atom

Is atom indivisible particle?


In the late of 19th century, subatomic particles, proton
(+1.60x10-19 C = 1+), neutron (neutral particle), and
electron (-1.60x10-19 C = 1-) were found.

1 Coulomb = 1 ampere of electrical current flows for 1 second

Mass Charge
Particle Grams Atomic Mass Coulombs Electronic
Unit Charge Unit
Proton 1.67 x 10-24 1.007276 +1.60x10-19 1+
Neutron 1.67 x 10-24 1.008665 0 0
Electron 9.11 x 10-28 0.0005486 -1.60x10-19 1-

Mass of an atom is primarily determined by the number of


protons and neutrons in its nucleus

Nucleus is so tiny with the density of about 1014 g/cm3

Number of proton in nucleus = atomic number of the atom

Atom is neutral!!!

Number of proton = number of electron

An atom represented symbolically by writing its mass number


as a superscript and its atomic number as a subscript
12
A
Z X

Z = atomic number
= number of protons
= number of electrons in (neutral) atom
A = mass number
A – Z = number of neutrons
12
C
6 and 13
C
6 are isotopes of carbon

63
29 and Cu are isotopes of copper whose the masses are
Cu 65
29

62.9298 and 64.9278 u, respectively, and their abundance are


69.09 % and 30.91 %. What is the average atomic mass of this
element?

Atomic number and the modern periodic table

See the modern periodic table

13
Formation of ionic compound

When two or more substances combine to form a single


product the reaction sometime called a combination reaction

2Na(s) + Cl2(g)  2NaCl(s)

Atom of sodium loses one electron, which is transferred to a


chlorine atom

Sodium atom loses one electron, become positive ion, with the
charge 1+ called a cation, written as Na+
Chlorine atom gains one electron, become negative ion,
chloride ion, with the charge 1- called an anion, written as Cl-
NaCl is an ionic compound

Metals tend to react with nonmetals to form ionic


compounds

Group number
IA IIA IIIA IVA VA VIA VIIA
Li+ Be2+ C4- N3- O2- F-
Na+ Mg2+ Al3+ Si4- P3- S2- Cl-
K+ Ca2+ Se2- Br-
Rb+ Sr2+ Te2- I-
Cs+ Ba2+

The transition metals are able to form more than one ion

Cations formed by some transition elements


14
Chromium Cr2+ Gold Au+
Cr3+ Au3+
Manganes Mn2+ Zinc Zn2+
Mn3+ Cadmium Cd2+
Iron Fe2+ Mercury Hg22+
Fe3+ Hg2+
Cobalt Co2+ Tin Sn2+
Co3+ Sn4+
Nickel Ni2+ Lead Pb2+
Copper Cu+ Pb4+
Cu2+ Bismuth Bi3+
Silver Ag+

Rules for writing formulas for ionic compound


1. The positive ion is always written first in the formula.
2. The total of positive charges equals the total number of
negative charge; the formula unit must be electrically
neutral.
3. The smallest set of subscripts that give electrical neutrality
is always chosen.

Example:
The compound form from Ca2+ and Cl- is CaCl2
The compound form from Ca2+ and O2- is CaO
The compound form from Na+ and O2- is Na2O
The compound form from Al3+ and O2- is Al2O3
Ions can contain more than one atom

Cations
NH4+ ammonium
15
H3O+ hydronium

Anions
CO32- carbonate ClO4- perchlorate
HCO3- hydrogen carbonate ClO3- chlorate
(bicarbonate) ClO2- chlorite
C2O42- oxalate ClO- or OCl- hypochlorite
CN- cyanide PO43- phosphate
- 2-
NO3 nitrate HPO4 hydrogen phosphate
NO2- nitrite H2PO4- dihydrogen phosphate
OH- hydroxide CrO42- chromate
SO42- sulfate Cr2O72- dichromate
HSO4- hydrogen sulfate MnO4- permanganate
(bisulfate) C2H3O2- acetate
SO32- sulfite
HSO3- hydrogen sulfite
(bisulfite)

Writing the formula of calcium phosphate: Ca3(PO4)2

Formation of molecular (non-ionic) compound

The nonmetals elements can react with each other to form


molecular (non-ionic) compound.
2H2(g) + O2(g)  2H2O(l)
Simple compound of nonmetals with hydrogen

Group IVA Group VA Group VIA Group VIIA


CH4 NH3 H2O HF
16
SiH4 PH3 H2S HCl
GeH4 AsH3 H2Se HBr
SbH3 H2Te HI

Simple compound of nonmetals with oxygen

Group IIIA Group IVA Group VA Group VIA


B2O3 CO2 N2O3 SO2
SiO2 N2O5 SO3
GeO2 P2O3 SeO2
P2O5 SeO3
As2O3 TeO2
As2O5 TeO3
Sb2O3
Sb2O5

17
Some properties of ionic and molecular (nonionic) compound:

1. Melting point: ionic compounds have a high melting point.


NaCl, an ionic compound, melts at 800 oC.
eicosane (C20H42), one of the compounds in a mixture of
substance called paraffin wax, a non-ionic compound, melts
at 37 oC.

2. Ionic compounds can be crushed become powder, not with


non-ionic compounds.

3. Ionic compounds dissolve in water; non-ionic compounds


dissolve in liquids such as gasoline and paint thinner.

4. Electrical conductivity:
- Both ionic and non-ionic compounds in the solid form do
not conduct electricity.
- Molten non-ionic compounds do not conduct electricity,
molten ionic compounds does.

Naming chemical compound

2 groups of compounds:
Inorganic compounds: their structures are not determined
primarily by linking together of carbon atoms.
Organic compounds: their structures primarily determined by
linking together of carbon atoms.

18
Names of anions:
IVA VA VIA VIIA_____
C4- carbide N3- nitride O2- oxide F- fluoride
Si4- silicide P3- phosphide S2- sulfide Cl- chloride
As3- arsenide Se2- selenide Br- Bromide

Common (systematic) name:


For metals that occur in one oxidation state:
NaCl sodium chloride
SrO strontium oxide
Al2S3 aluminium sulfide
For metals that occur in more than one oxidation state:
Cr3+ chromic ion CrCl3 chromic chloride
Cr2+ chromous ion CrCl2 chromous chloride
Fe3+ ferric ion Fe2S3 ferric sulfide
Fe2+ ferrous ion FeS ferrous sulfide
2+
Cu cupric ion CuO cupric oxide
Cu+ cuprous ion Cu2O cuprous oxide
Sn4+ stannic ion Sn(SO4)2 stannic sulfate
Sn2+ stannous ion SnSO4 Stannous sulfate
3+
Co cobaltic ion Co2(CO3)3 cobaltic carbonate
Co2+ cobaltous ion CoCO3 cobaltous carbonate

Stock name (system):


FeBr3 iron(III) bromide Co2(CO3)3 cobalt(III) carbonate
FeBr2 iron(II) bromide CoCO3 cobalt(II) carbonate
Cu2SO4 copper(I) sulfate Pb(C2O4)2 lead(IV) oxalate
CuSO4 copper(II) sulfate PbC2O4 lead(II) oxalate

19
Non-metal compounds
NO2 nitrogen dioxide CO carbon monoxide
N2O4 dinitrogen tetroxide CO2 carbon dioxide
N2O5 dinitrogen pentoxide
PCl3phosphorus trichloride
PCl5phosphorus pentachloride

Acids (when they dissolved in water)


HF(aq) Hydrofluoric acid
HCl(aq) Hydrochloric acid
HBr(aq) Hydrobromic acid
HI(aq) Hydroiodic acid
H2S(aq) Hydrosulfuric acid

Oxoacids
H2SO4 sulfuric acid SO42- sulfate
H2SO3 sulfurous acid SO32- sulfite
HNO3 nitric acid NO3- nitrate
HNO2 nitrous acid NO2- nitrite

HClO4 perchloric acid ClO4- perchlorate


HClO3 chloric acid ClO3- chlorate
HClO2 chlorous acid ClO2- chlorite
HClO hypochlorous acid ClO- hypochlorate

20
CHEMICAL REACTIONS IN AQUEOUS
SOLUTION
Solution:
Concentrated: a large amount of solute dissolved in solvent
Dilute: small amount of solute dissolved in solvent
Saturated: contains maximum solute can dissolved
Unsaturated: contains less than maximum solute can
dissolved
Supersaturated: contains more than maximum solute can
dissolved (this solution is not stable).

Electrolytes
Water is very poor conductor.
When NaCl dissolved in water, the solution will conduct
electricity. The compounds that have the same property
with NaCl said to be electrolytes.
In water NaCl dissociates. The ions surrounded by water
molecules (in the reaction indicated by aq after the
formula of the ions), and said to be hydrated.
NaCl(s)  Na+(aq) + Cl-(aq)
HCl(g) + H2O  H3O+(aq) + Cl-(aq)
These reactions called ionization reactions
For simplicity, labels (s), (aq) and (g) are very often leaved off

Strong and weak electrolytes

Compare the conductivity solutions of C12H22O11 (sugar),


NaCl, HCl, Ca(NO3)2, HC2H3O2 (acetic acid), NH3 (ammonia),
HCN (hydrogen cyanide)
C12H22O11 (sugar) is not electrolyte (non-electrolyte)
21
HC2H3O2 (acetic acid), NH3 (ammonia), HCN (hydrogen
cyanide) are weak electrolytes
NaCl, HCl, Ca(NO3)2 are strong electrolytes

Dissociation of weak electrolytes

% dissociated in 1.00 M solution


HC2H3O2 + H2O  H3O+ + C2H3O2- 0.42
NH3+ H2O  NH4+ + OH- 0.42
HCN + H2O  H3O+ + CN- 2.0 x 10-3

HC2H3O2 + H2O H3O+ + C2H3O2-


NH3+ H2O NH4+ + OH-
HCN + H2O H3O+ + CN-

Reaction between ions


AgNO3(aq) + NaCl(aq)  AgCl(s) + NaNO3(aq)

In the solution electrolyte will dissociates


Ag+(aq) + NO3-(aq) + Na+(aq) + Cl-(aq)  AgCl(s) + Na+(aq) + NO3-(aq)

There are no change the ions of NO3-(aq), Na+(aq) in the


solution, so the reaction can be written as
Ag+(aq) + Cl-(aq)  AgCl(s)

22
Acid – base reactions

Acid: - has sour taste


- can changes color of blue litmus paper to become pink
- a substance that in aqueous solution increases the
concentration of hydronium ion, H3O+ (Arrhenius
definition).
Base: - has bitter taste
- can changes color of pink litmus paper to become blue
- a substance that in aqueous solution increases
hydroxide ion, OH- (Arrhenius definition).

HC2H3O2 + H2O H3O+ + C2H3O2-


More simply:
HC2H3O2 H+ + C2H3O2-

Polyprotic acids: H2S, H2SO4, H2CO3, H3PO4,

Bases: NaOH, KOH, Ca(OH)2, Mg(OH)2


Neutralization reactions
H3O+(aq) + OH-(aq)  2H2O
H+(aq) + OH-(aq)  H2O
Neutralization stomach acid:
Mg(OH)2(s) + 2H+(aq)  Mg2+(aq) + 2H2O
Al2O3(s) + 6H+(aq)  2Al3+(aq) + 3H2O
Removing rust:
Fe2O3(s) + 6H+(aq)  2Fe3+(aq) + 3H2O

Acid salts formation:


23
2NaOH(aq) + H2SO4(aq)  Na2SO4(aq) + 2H2O

NaOH(aq) + H2SO4(aq)  NaHSO4(aq) + H2O

Principle of the reactions

Metathesis reactions (double replacement or changes the


partners)
- precipitation:
Ag+(aq) + Cl-(aq)  AgCl(s)
Ca2+(aq)+ C2O42-(aq)  CaC2O4(s)

- weak electrolyte is formed:


H3O+ + NaC2H3O2  HC2H3O2 + H2O + Na+
H+ + NaC2H3O2  HC2H3O2 + Na+

- gas is formed:
CaCO3(s)+ 2HCl(aq)  CaCl2(aq) + H2O + CO2(g)
CaCO3(s)+ 2H+(aq)  Ca2+(aq) + H2O + CO2(g)

Oxidation – reduction reactions

From the time that oxygen was discover, the term oxidation
has been associated with the reaction of this compound with
another compounds or elements to form oxides compounds.

24
Since known that iron oxide could be broken down (reduced)
to give the free metal, recovery of metal from its oxide known
as reduction.
4Fe(s) + 3O2(g)  2Fe2O3(s)

Fe loses 3 electrons to become Fe3+


Each O in O2 molecule gains 2 electrons to become O2-

Oxidation is the loss of electron(s) from a substance


Reduction is the gain of electron(s) from a substance

2Mg(s) + O2(g)  2MgO(s)

product of this reaction is an ionic compound, MgO, contains


Mg2+ and O2-, so the reaction can be considered as

Mg  Mg2+ + 2e (oxidation)
O2 + 4e  2O2- (reduction)

O2 is oxidizing agent, it takes electrons from the substance


that is oxidized. O2 itself is reduced in fact.
Mg is reducing agent, it gives electrons to the substance that
is reduced. Mg itself is oxidized in fact.

Oxidation number
are numbers (either positive or negative) that we assign to
atoms in a compound so we can follow the changes that take
place in redox reaction

25
The oxidation number are assigned according to a set of rules

Rules for assigning oxidation numbers

1. The oxidation number of any element in its elemental form


is zero (Ne, H2, N2, P4, S8, Fe, Cu, etc.)

2. The oxidation number of any monoatomic ion (an ion


composed of only one atom) is equal to the charge of the
ion.

3. The sum of all the oxidation numbers of all the atoms in a


compound is zero. For polyatomic ions, the sum of the
oxidation numbers must equal to the charge of the ion.

4. Fluorine has an oxidation number of –1.

5. Hydrogen has an oxidation number of +1.

6. Oxygen has an oxidation number of –2.

Examples: FeCl3
KNO3
H2O2
Fe2(SO4)3
Cr2O72-
ClO3-

26
Identifying oxidation and reduction in a reaction

14HCl + K2Cr2O7  2KCl + 2CrCl3 + 3Cl2 + 7H2O


+1 -1 +1 +6 -2 +1 -1 +3 -1 0 +1 -2

Redox reactions
Mg  Mg2+ + 2e x2 (oxidation)
O2 + 4e  2O2- x1 (reduction)
2Mg + O2  2MgO (redox)

Solubility rules

1. All salts of the alkali metals are soluble


2. All salts of the ammonium ion, NH4+, are soluble
3. All salts of the nitrate ion (NO 3-), chlorate ion (ClO3-),
perchlorate ion (ClO4-), and acetate ion (C2H3O2-) are
soluble
4. All salts of the chlorides, bromides, and iodides are soluble,
except those Ag+, Pb2+, and Hg22+
5. All salts of the sulfates (SO42-) are soluble, except those of
Ca2+, Sr2+, Ba2+, and Pb2+
6. All metals oxides are insoluble, except for those of the
alkali metals, Ca2+, Sr2+, and Ba2+
7. All hydroxides are insoluble, except for those of the alkali
metals, Ca2+, Sr2+, and Ba2+
8. All carbonates (CO32-), phosphates (PO43-), sulfides (S2-),
and sulfites (SO32-) are insoluble, except for those of NH4+
and the alkali metals

27
Ion-electron method for balancing redox reaction equations
for acidic solution

Step 1. Devide the skeleton equation into half-reactions


Step 2. Balance atoms other than oxygen and hydrogen
Step 3. Balance the oxygen in each half-reaction by adding
water molecules to the side that needs oxygen atoms.
Add one H2O for each of oxygen needed
Step 4. Balance the hydrogen atoms in each half-reaction by
adding H+ to the side needs hydrogen. Add one H+ for
each hydrogen needed
Step 5. Balance the charge in each half-reaction by adding
electrons to the appropriate side
Step 6. Multiply each half-reaction by appropriate factors to
make the number of electrons gained equal to the
number lost.
Step 7. Add the two half-reactions together
Step 8. Cancel anything that is the same on both side of the
equation

Example: reaction between HCl and KMnO4 solutions will


produce Cl2 and Mn2+. Show the balanced ionic and
molecular reaction.

In water, both of HCl and KMnO4 will dissociated to be their


ions. The skeleton equation is:
Cl- + MnO4-  Cl2 + Mn2+

Step 1. Cl-  Cl2


MnO4-  Mn2+
28
Step 2. 2Cl-  Cl2
MnO4-  Mn2+

Step 3. 2Cl-  Cl2


MnO4-  Mn2+ + 4H2O

Step 4. 2Cl-  Cl2


MnO4- + 8H+ Mn2+ + 4H2O

Step 5. 2Cl-  Cl2 + 2e


MnO4- + 8H+ + 5e  Mn2+ + 4H2O

Step 6. (2Cl-  Cl2 + 2e )x5


(MnO4- + 8H+ + 5e  Mn2+ + 4H2O) x 2

Step 7. 10Cl- + 2MnO4- + 16H+  2Mn2+ + 8H2O + 5Cl2

The ionic reaction is:


10Cl- + 2MnO4- + 16H+  2Mn2+ + 8H2O + 5Cl2

The molecular reaction:


10Cl- + 2MnO4- + 16H+  2Mn2+ + 8H2O + 5Cl2

10Cl- +10H+ + 2MnO4- + 2K+ + 6H+ + 6Cl- 


2Mn2+ + 4Cl-+ 8H2O + 5Cl2 + 2K+ + 2Cl-

10HCl + 2KMnO4 + 6HCl  2MnCl2+ 8H2O + 5Cl2 + 2KCl

16HCl + 2KMnO4  2MnCl2+ 8H2O + 5Cl2 + 2KCl


=====================6/11/15
29
Redox reaction in basic solution

Step 1. Balance the reaction as it occurred in an acidic solution


Step 2. For eah H+, add OH- to both side of the equation
Step 3. Combine H+ and OH- to form H2O
Step 4. Cancel H2O that are the same on both sides

Example: reaction between KMnO4 and FeSO4 in basic


solutions will produce Ferric compound and
insoluble MnO2. Show the balanced ionic and
molecular reaction.

KMnO4 + FeSO4  MnO2 + Fe3+

Following the procedure as for acidic solution, will give


oxidation and reduction equations:
MnO4- + 4H+ + 3e  MnO2 + 2H2O
Fe2+  Fe3+ + e

Now, follow the procedure of redox reaction in basic solution

MnO4- + 4H+ + 4OH- + 3e  MnO2 + 2H2O + 4OH-


MnO4- + 4H2O + 3e  MnO2 + 2H2O + 4OH-

MnO4- + 2H2O + 3e  MnO2 + 4OH- x 1 (reduction)


Fe2+  Fe3+ + e x 3 (oxidation)
MnO4- + 2H2O + 3Fe2+  MnO2 + 4OH- + 3Fe3+ (ionic-redox)

KMnO4 + 2H2O + 3FeSO4  MnO2 + KOH + Fe2(SO4)3 + Fe(OH)3

6KOH + Fe2(SO4)3  3K2(SO4) + 2Fe(OH)3


30
Examples:

1. How would you prepare a solution of 2.00 % (w/w) NaCl in


water?

2 % (w/w) NaCl means 2.00 g NaCl in 100.00 g solution


So, to prepare the solution, mix 2,00 g NaCl and 98.00 g
water. Because of the density of water is 1.00 g/mL, we can
use 98.00 mL.

2. A 500 L sample of air with a density of 1.20 g/L was found


to contain 2.40 x 10-3 g of the pollutant SO2. What is the
concentration of the pollutant express in % by mass and in
part per million (ppm) by mass

% means 1/100
ppm means 10-6

Mass of air = its volume x density


= 500 L x (1.20 g/1.00 L) = 600 g
% by mass = (mass of SO2/mass of air) x 100 %
= (2.40 x 10-3 g/600 g) x 100 %
= 4.00 x 10-4 %

ppm by mass = (mass of SO2/mass of air) x 106 ppm


= (2.40 x 10-3 g/600 g) x 106 ppm
= 4.00 ppm

31
3. What is mass of aluminium (ion) in 100 mL of solution of
0.240 M Al2(SO4)3?

Any reaction must fulfill the law of conservation of mass,


and conservation of ion.

Aluminium sulfate is an ionic compound. This compound will


dissociate in water according to the reaction
Al2(SO4)3  2Al3+ + 3SO42-
Therefore Al3+ concentration = (2/1) x 0.240 M
= 0.480 M
= 0.480 mol/L
= 0.480 mol/1000 mL
= 0.0480 mol/100 mL
this means in 100 mL of the solution contain 0.0480 mol Al3+
ion, or 0.0480 mol x 26.98 g/mol = 1.30 g

4. How many mL of 0.350 M CaCl2 are needed to give 1.25 g


of Cl2 gas in the reaction
10Cl- + 2MnO4- + 16H+  2Mn2+ + 8H2O + 5Cl2

From the atomic mass table, the formula mass (or relative
molecular mass) of Cl2 is 70.9 g/mol, therefore
Mol amount of 1.25 g Cl2 = 1.25 g /(70.9 g/mol)
= 1.76 x 10-2 mol
Cl- needed = (10/5) x 1.76 x 10-2 mol
= 3.52 x 10-2 mol
Solution of 0.350 M CaCl2 contains 0.700 mol Cl-/1000 mL.
Solution of CaCl2 needed = 3.52x10-2 mol/(0.700mol/1000
mL)
= 50.3 mL
32
13/9/15
Chemical analysis and titration

Chemical analysis is an experimental determination of either


qualitative or quantitative of a chemical in a sample.

Titration is an analytical procedure to measure the amount of


a solution needed to react exactly with the content of another
solution (also called volumetric analyses).

Examples:

1. A white powder was known to be a mixture of NaCl and


Na2SO4. A sample of the powder weighing 1.244 g was
dissolves in water and a solution of Ba(NO3)2 was added
until the precipitation of BaSO4 was complete. The reaction
mixture was filtered carefully to be sure that none of the
precipitate was lost, and the BaSO4 was then dried and
found to weigh 0.851 g. What was the percentage by mass
of Na2SO4 in the original sample?

From the atomic mass table, the formula mass (or relative
molecular mass) of BaSO4 is known = 233.4 g/mol
Therefore, the mol number of BaSO4 = 0.851 g/(233.4 g/mol)
= 3.65 x 10-3 mol

BaSO4 formed from the reaction


Ba(NO3)2 + Na2SO4  BaSO4 + 2NaNO3
or Ba2+(aq) + SO42-(aq)  BaSO4(s)

33
Hence, the mol number of SO42- = the mol number of Na2SO4
= 3.65 x 10-3 mol

Relative molecular mass of Na2SO4 = 142.0 g/mol


So the mass of Na2SO4 = 3.65 x 10-3 mol x (142.0 g/mol)
= 0.518 g

% (w/w) Na2SO4 = (mass of Na2SO4/mass of sample) x 100 %


= (0.518 g/1.244 g) x 100 %
= 41.6 %
2. To measure the concentration of NaOH solution, a 20.00
mL of 0.100 M HCl was inserted into a beaker and a few
drops of phenolphtalein were added into the HCl solution.
A buret was filled with NaOH solution and used for titrate
the HCl solution. The titration required 18.47 mL of the
base in order to reach the end point. What is the molarity of
the NaOH solution?

Balanced chemical equation of the reaction


NaOH(aq) + HCl(aq)  NaCl(aq) + H2O

First calculate the moles number of HCl in 20.00 mL before


titration begun.

The moles number of HCl in 20.00 mL before titration =


20.00 mL x 0.100 mol/1000 mL = 2.000 x 10-3 mol

At the end point (the mol amount of HCl is in balance with the
mol amount of NaOH). The mol amount of NaOH =
(1/1) x 2.000 x 10-3 mol = 2.000 x 10-3 mol

34
Remember: M x V = mol number, or M = mol number/V

Therefore:
Molarity of NaOH = 2.000 x 10-3 mol/18,47 mL
= 0.1083 10-3 mol/mL
= 0.1083 mol/L

Do the same ways for any chemical analysis

Equivalent weights and normality

Acid-base reaction:
An equivalent of an acid is defined as the amount of acid that
furnishes 1 mol of H+
An equivalent of a base is defined as the amount of base that
furnishes 1 mol of OH-

Number of equivalent = number of mol x n

n = is a the number of H+ provided by 1 molecule of acid or


the number of OH- provided by 1 molecule of base

In any reaction,
the reaction is always in the equivalent ratio of 1 : 1

Example:
How many mol of NaOH can react with 0.1 mol H2SO4.
Compare the calculation using mol and equivalent systems.

35
Oxidation-reduction reaction:
An equivalent of an oxidizing or reducing agents in a redox
reaction is the amount of substance that gains or loses one mol
of electron.

Number of equivalent = number of mol x n

n = is the total number of electrons gained or lost by one


formula unit of substance (also can be calculated from the
change of oxidation number)
Examples:
1. How many equivalents are there per mole reagents in the
following reactions, show the calculations using the change
of oxidation number and the electrons are involved.
a. Ca(IO3)2  I-
b. NO3-  NH4+
c. KMnO4  MnO2
d. KMnO4  Mn2+

2. How many mole FeSO4 can react with 0.1 mole KMnO4.
Compare the calculation using mole and equivalent systems.

Normality = number of equivalents/1 liter of solution

N=Mxn

VA.NA = VB.NB

36
Examples:
1. How many grams of K2Cr2O7 are needed to prepare 100 mL
of a 0.100 M K2Cr2O7, if in the reaction, the chromium
converted to be Cr3+ (the reaction in acid solution)

2. How many mL of 0.20 M K2Cr2O7 are needed to react with


60 mL of 0.40 M H2C2O4 (the reaction in acid solution), and
how many grams CO2 will be produced as the result of
conversion of H2C2O4

THE pH CONCEPT

Hydrogen ion and hydroxide ion in aqueous solution may


range from 10 M to 10-14 M, so it is frequently necessary to
specify their concentrations, and a logarithmic notation has
been devised to simplify the expression for very low
concentration. In general, for low concentration of X, the
quantity pX is defined as:
pX = log X
Hence, to specify low concentration of hydrogen ion in a
solution, it is defined:
pH = log [H+]
For a solution contains 10-3 M of hydrogen ion, then
pH = log [H+] = log 103 = 3
37
To specify low concentration of hydroxide ion in a
solution, it is defined:
pOH = log [OH]
Then, for a solution contains 10-3 M of hydroxide ion,
pOH = log [OH] = log 103 = 3

Water can dissociate to produce H+ and OH, where their


multiplication is Kw = 1 x 1014 M2
Kw = [H+][OH]
log Kw = (log [H+]) + (log [OH])
pKw = pH + pOH = log 1 x 1014 = 14
Pure water has the same concentration of H+ and OH, so it
has pH = 7
Acid solution has pH < 7, and basic solution has pH > 7

When weak acid is dissolved in water, only small part of


the acid dissociates to produce its ions
HC2H3O2 + H2O H3O+ + C2H3O2
acid base acid base
In this case acid constant:
Ka = [H3O+][C2H3O2]/[HC2H3O2] = 1.8x10-5 M
Hence, when concentration of the acid is 0.1 M, level of its
dissociation (α) can be calculated as follows:
(0.1 α x 0.1 α)/0.1 (1- α) = 1.8x10-5
Due to this compound is weak acid, 1- α  1, so
α2 = 1.8x10-4 or α = 1.34 x 10-2 or [H3O+] = 1.34 x 10-3
And pH of this solution is:
pH = -log 1.34 x 10-3 = 2.87

38
When into a weak acid solution is added its salt, then the
mixture will has a buffer property (it means that the pH
relatively constant when small amount of acid or base is
added). As an example, if we have a solution contains 0.1
M of acetic acid and 0.1 M of sodium acetate,
Ka = [H3O+][C2H3O2]/[HC2H3O2]
[H3O+] = Ka [HC2H3O2]/[C2H3O2]
-log [H3O+] = -log (Ka [HC2H3O2]/[C2H3O2])
pH = -log (1.8x10-5 x 0.1/0.1) = 4.74

If into this solution, 0.01 M of NaOH is added, then


pH = -log (1.8x10-5 x 0.09/0.11) = 4.83

If into this solution, 0.01 M of HCl is added, then


pH = -log (1.8x10-5 x 0.11/0.09) = 4.66

4/12/15

39
Chapter 11

PROPERTIES OF GASES

Matter can exist in three different physical forms or states i.e.


solid, liquid and gas
Intermolecular forces (attraction or repulsion) between gas
particles are weak, cause independent movement and, physical
behavior controlled by:
volume, pressure, temperature and number of mole

Gas occupy entire volume of container


Gases mix freely with one another in the container, and
volume of each gas is the same as the volume of container

Pressure  force per unit area


100 lb force exerted on a piston whose total area 100 in2

100 lb lb
Pr essure  2
 1 2  1 psi
100 in in
SI unit of pressure is the pascal (Pa)

1 Pa = 1 N/m2

1 atm = 760 mm Hg = 760 torr = 101,325 Pa

40
Manometer pictures
Determination of pressure using manometer
Robert Boyle’s experiment (1662): If the temperature of a gas
is held constant, its volume is inversely proportional
to the pressure.
V α 1/P (at constant temperature)
V = constant /P
P x V = constant
Jacques Alexander Charles’s experiment (1787): At constant
pressure, volume of a gas is directly proportional to
its temperature, provided the temperature is
expressed in Kelvin.
VαT (at constant pressure)
V = constant x T
V /T = constant
Joseph Gay-Lussac’s experiment: At constant pressure,
volume of a gas is directly proportional to its
temperature, provided the temperature is expressed in
Kelvin.
PαT (at constant volume)
P = constant x T
P /T = constant
The combined gas law:
PV/T = constant
PV/T = nR
PV = nRT (the ideal gas law)
P i x V i / Ti = P f x V f / Tf

41
STOICHIOMETRY OF GASEOUS REACTION

2C4H10 (g)+ 13O2 (g)  8CO2 (g)+ 10H20 (l)


4.50 L ?L ?L

How many liters 1 mole gas at STP?

DALTON’S LAW OF PARTIAL PRESSURE

PT = pa + pb + pc + .........

Example: If 200 mL N2 at 25 oC and 250 torr are mixed with


350 mL O2 at 25 oC and 300 torr in the volume of
300 mL, what would be the final pressure?

GAS PRESSURE OVER WATER

PT = pgas + pwater

pgas = PT - pwater

GRAHAM’S LAW OF EFFUSION


Rate of effusion 
1
d

Rate of effusion A
dB MB
——————— = dA = MA
Rate of effusion B

42
Dalton’s law of partial pressure:

pA = xAPT

Moles number of A
xA = —————————————————
Total moles number of gas in the mixture

REAL GAS

The ideal gas law: PV = nRT


V = nRT/P
Whe the pressure extremely high ( P = ∞), V = 0
From experiment, V is never became 0
J.D. van der Waals (1837 -1923) gave a correction:
Vmeas = Videal + nb
Videal = Vmeas – nb
Real gas has a lower pressure compare to the ideal gas.
J.D. van der Waals (1837 -1923) gave a correction:
Pideal = Pmeas + n2a/V2
Combination of the equations:
nRT/Videal = Pmeas + n2a/V2
Pmeas = nRT/(Vmeas – nb) - n2a/V2
P = nRT/(V – nb) - n2a/V2
P = RT/(Vm – b) - a/Vm2
(P + n2a/V2)(V – nb) = nRT
(P + a/Vm2)(Vm – b) = RT

43
CHEMICAL THERMODYNAMICS

What is it that determines whether or not a chemical or


physical changes is possible?

Thermodynamics is basically concerned with the energy


changes that accompany chemical or physical processes.

Some common terms:


System and surroundings
State of system and state function
Isobar, isothermal and adiabatic changes
Internal energy, U

First law of thermodynamic: if a system undergoes some


series of changes that ultimately brings it back to its
original state, the energy change is zero, E = 0

E = Efinal – Einitial
E = Eproducts – Ereactants
E = q + w
Example:
A system absorbs 50 J of heat and does 30 J of work
Esystem = (+50 J) + (-30 J)
= + 20 J
Esurroundings = (-50 J) + (+30 J)
= - 20 J
Esystem + Esurroundings = 0
q positive (q > 0): heat is added to the system
44
q negative (q < 0): heat is evolved by (removed from) the
system
w positive (w > 0): work is done on the system; energy is
added to the system
w negative (w < 0): work is done by the system; energy is
remove from the system

Work in physical and chemical processes

work = force x distance


w = F h
A
= F h A
F
= A (A h)
= P V
= P (Vfinal – Vinitial)

wsurroundings = P V
wsystem = -P V

How many Joule is the work done by a system when it’s


expanded from 1 liters to 100 liters opposes pressure equal
to zero?

How many Joule is the work done by a system when it’s


expanded from 2 liters to 10 liters opposes pressure equal
to 1 atm?

Heats (enthalpy) of reaction

45
Esystem = q - P V

If during the change of state, the pressure is constant

Esystem = qp - P (Vfinal – Vinitial)


qp = E + P Vfinal - P Vinitial
= (Efinal + P Vfinal) – (Einitial + P Vinitial)
= Hfinal - Hinitial

qp = H

Bond energy and enthalpy (heats) of reactions

Bond energy: the amount of energy needed to break a


chemical bond to produce electrically neutral fragments
(atoms)

Heats (enthalpy) of formation: the amount of energy


needed or liberated in a chemical reaction whereas a
compound formed from its elements.

Energy (enthalpy) of chemical reaction: the amount of


energy needed or liberated in a chemical reaction whereas
the reactants converted to the products.

Enthalpy

C(g) + 4H(g)
46
H2 =
+872 kJ
H3= ?
C(g) + 2H2(g)
H1 =
+715 kJ

C(s,graphite) + 2H2(g)

Hf =
CH4(g) -74.9 kJ

Hf = H1 + H2 + H3


H3 = Hf - H1 - H2
H3 is the energy needed to break all 4 C-H bond

What is (are) the factor(s) that control spontaneity?

The second law of thermodynamics: in any spontaneous


change, there is always an increase the entropy (tendency
toward disorder) of the universe.

If the entropy increase, S > 0, or S = +


The universe is an isolated system
Our system can be isolated, closed or open system!
Some reaction can happen spontaneously with H = -
Some reaction can happen spontaneously with H = +
Some reaction can happen spontaneously with S = +
Some reaction can happen spontaneously with S = -
47
Gibbs combines these phenomena to determine the
spontaneity with single thermodynamics quantity, G,
called the Gibbs free energy, defined as

G = H – TS
G = H – TS

Any process will spontaneously happen if the Gibbs


free energy decrease, G < 0, or G = –

Goreaction = Horeaction – TSoreaction


Horeaction = Hof, products – Hof, reaactants
Soreaction = Soproducts – Soreaactants

Goreaction = Gof, products – Gof, reaactants

48
CRYSTAL STRUCTURE OF INORGANIK
COMPOUND

In general, solid phase of inorganic compounds (NaCl,


KBr, CuCl2, FeCl3, etc.) are in crystal form.
● ●
● ●
c

β
α
● a γ ●
● ● b

Properties of the unit cells of the seven crystal systems


System Edge lengths Angels
Cubic a=b=c α=β=γ=90o
Tetragonal a=b≠c α=β=γ=90o
Orthorombic a≠b≠c α=β=γ=90o
Monoclinic a≠b≠c α=β=90o≠γ
Triclinic a≠b≠c α≠β≠γ
Rhombohedral a=b=c α=β=γ≠90o
Hexagonal a=b≠c α=β= 90o; γ=120o

There are 3 kinds of lattice of cubic unit cells:


1. Simple cubic (frozen of oxygen)
2. Body centered cubic (chromium, iron, tungsten)
3. Face centered cubic (nickel, copper, silver, gold,
aluminium).

49
The crystal lattices could be determined by X-ray
diffraction method where the Bragg equation is fulfilled
2d sinθ = nλ
d is the spacing between the successive layers that are
reflecting the X ray,
θ is the angle at which the X ray enter and leave the
particular layers,
n is integer (1, 2, 3, etc.)
λ is the wavelength of the X ray.

Soil contains crystals of inorganic compounds hence


type of soil can be determined by X-ray diffraction
method

Base on X-ray diffraction method, it is known that


metallic sodium crystallizes with a body-centered cubic
lattice. The element has density of 0.97 g/cm3. What is
the length of the edge of the unit cell in Na expressed in
nanometers?
● ● B
● ●
c

β
α
● a ● C
A● ● b
D

8 corners x 1/8 Na per corner = 1 Na


1 Na in the center = 1 Na
Total Na per unit cell = 2 Na
(AB)2 = (AC)2 + (BC)2
(AC)2 = (AD)2 + (CD)2
50
(AD) = (CD) = (BC)
(AC)2 = (BC)2 + (BC)2 = 2(BC)2
(AB)2 = 2(BC)2 + (BC)2 = 3(BC)2
(AB) = 4r
(AB) 2 (4r) 2
(BC)  
3 3
3
23.00g 6.02x1023   4r  2 
Volum 1 mol Na = 0.97g/cm 3

2 

3


Hence the radius of Na atom (=r) can be determined.

51

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