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AS Revision

Physical Chemistry

Chapter 1: Atoms, Molecules & Stoichiometry


Definition
Relative atomic mass

Relative isotopic mass

Relative molecular mass

Relative formula mass

Example

Determination of Ar from mass spectra


The mass spectrum of a sample of chromium, Cr, is shown below.

Naturally occurring gallium, Ga exists as two isotopes,


Determine the percentage abundance of each isotope.

69

Ga and

71

Ga.

Use the information from this mass spectrum to calculate the relative atomic
mass of chromium. Give your answer to 3 significant figures.

Stoichiometry calculation
How many atoms are there in each of the following?
(a) 0.100mol of C3H8
[1]
(b) 0.0100mol of C8H18

It has been estimated that only 0.35g of the element astatine exist in the
earth's crust whose volume is 1.5x1019m3. On average, how many astatine
atoms are present in each cubic metre of the earth's crust?

3.30g of a compound consisting of carbon, hydrogen and oxygen only was When heated, potassium chlorate decomposes into solid potassium chloride
analysed and found to contain 1.29g of carbon and 0.29g of hydrogen. and oxygen gas. If 5.00g of potassium chlorate produced 3.04g of
Calculate its empirical formula.
potassium chloride in this way, determine the empirical formula of
potassium chlorate and write a balanced equation for the reaction.

FB1 is 0.023mol dm-3 potassium manganate (VII), KMnO4.


You are to determine the concentration of hydrochloric acid, which supplies
FB2 is aqueous ethanedioic acid, H2C2O4, made by dissolving the hydrated the H+ ions in the following reaction.
salt, H2C2O4.2H2O.
IO3- (aq) + 5I- (aq) + 6H+ (aq) 3H2O (l) + 3I2 (aq)
42.50cm3 of FB2 is pipetted into the 250cm3 graduated flask, labeled FB3
and make up with distilled water.
In the presence of an excess of IO3- ions and an excess of I- ions, the amount
of I2 liberated is directly proportional to the amount of H+ ions present and
25.0cm3 of FB3 is pipetted into a conical flask and titrate against FB1. can be determined by titration with sodium thiosulfate, Na2S2O3.
Volume titre found is 22.50cm3.
FA1 hydrochloric acid

(a) Calculate how many moles of KMnO4 were run from the burette into the
conical flask.

FA2 containing 15.0g dm-3 sodium thiosulfate, Na2S2O3.5H2O


25.0cm3 of FA1 is pipetted into the conical flask. Add to the flask 10cm 3 of
aqueous potassium iodate (V) and 10cm3 of aqueous potassium iodide.
There is an excess of each of these reagents. The liberated iodine is titrated
with FA2. Volume titre found is 22.50cm3.

(b) Put the correct number of electrons into each of the following halfequation to balance the electrical charges.

(c) Calculate how many moles of ethanedioate ions,C2O42-, reacted with the
KMnO4 run from the burette. Calculate the concentration, in mol dm-3,
of C2O42- in FB3.

(d) Calculate the concentration, in mol dm-3, of C2O42- in FB2.

(a) Calculate the concentration, in mol dm-3, of the sodium thiosulfate in


FA2.
FA2 contains 15.0g dm-3 Na2S2O3.5H2O.
[Ar: H, 1.0; O, 16.0; Na, 23.0; S, 32.1]

(b) Calculate how many moles of Na2S2O3 are contained in the volume of
FA2 used in titration.

(c) Calculate how many moles of iodine, I2 reacted with the Na2S2O3 in
above.
2Na2S2O3 (aq) + I2 (aq) Na2S4O6 (aq) + 2NaI (aq)

(e) Calculate the concentration, in g dm-3, of H2C2O4.2H2O in FB2.


[Ar: H, 1.0; C, 12.0; O, 16.0]
(d) Calculate how many moles of hydrochloric acid, HCl, reacted with an
excess of potassium iodate (V) and an excess of potassium iodide to
produce the amount of iodine calculated in above.
IO3- (aq) + 5I- (aq) + 6H+ (aq) 3H2O (l) + 3I2 (aq)

(e) Calculate the concentration, in mol dm-3, of HCl in FA1.

Hydrocarbons are compounds of carbon and hydrogen only. Hydrocarbon Z A hydrocarbon of volume 20cm3 is exploded in 120cm3 of oxygen gas. The
is composed of 80% carbon and 20% hydrogen.
products of reaction are then allowed to pass through a solution of sodium
(a) Calculate the empirical formula of the hydrocarbon Z.
hydroxide which caused a reduction in final volume of gas mixture as much
as 40cm3, final volume of gas mixture is 50cm3. Determine the molecular
formula of the hydrocarbon.

(b) The molar mass of hydrocarbon Z is 30.0g mol-1. Deduce the molecular
formula of this hydrocarbon.

(c) When 50cm3 of hydrocarbon Y is burnt, it reacts with exactly 300cm3


of oxygen to form 200cm3 of carbon dioxide. Water is also formed in
this reaction. Deduce the equation for this reaction.

Chapter 2: Atomic Structure


Calculate no. of protons, neutrons and electrons in
40

K+

No. of P =
No. of N =
No. of E =
Isotopes

14

N3-

No. of P =
No. of N =
No. of E =

19

No. of P =
No. of N =
No. of E =
Examples

Size of atomic radius when


Across period

Move down a group

Ionisation energy when


Across period

Move down a group

Explanation for
1st I.E Be B (Period 2)

1st I.E N O (Period 2)

1st I.E Mg Al (Period 3)

1st I.E P S (Period 3)

Electronic configuration

Definition for orbital


Orbital s

Orbital p

Orbital d and so on

Aufbau Principle

Hunds Principle

Pauli Principle

Na
Mg
Al

Si
P
S
Cl
Ar
K
Ca
Sc

Sc3+

Ti

Ti4+

V
Cr
Mn
Fe
Co
Ni
Cu

Fe2+

Fe3+

Zn

The table below shows the first five ionisation energies for five elements The sketch graph shows the logarithm (log10) of successive ionisation energies
of aluminium plotted against the number of electrons removed. Use this sketch
(A to E).
graph to answer the following questions.
(a) State which group each of these elements belongs to.
Element

Ionisation energy / kJ mol1


1st

2nd

3rd

4th

5th

786

1580

3230

4360

16 090

418

3070

4600

5860

7975

1090

2350

4610

6220

37 830

548

1060

4120

5440

6908

577

1980

2960

6190

8200

(b) Explain the reasoning behind your answer for element C.


(a) Explain why the first three electrons are relatively easy to remove.
(b) Why is there a sharp rise in ionisation energy when the fourth electron is
removed?
(c) What information does the graph give about the electronic structure of
aluminium?
(d) Give the equation for the ionisation energy marked X (the 3rd ionisation
energy).

Chapter 3: Chemical Bonding


Ionic bonding
Dot and cross diagram

MgO

Physical properties:

Covalent bonding
Dot and cross diagram
Single bond
NH3

CaCl2

Lattice structure MgO

Double bond
CO2

Triple bond
N2

Coordinate/dative bond
NH4+

Al2Cl6

NH3.BF3
Summary

No. of bonding pair


2
3
2
3
4
5
6
Physical properties:

No. of lone pair


0
0
2
1
0
0
0

Geometry

Bond angle

Example

bond
In the formation of a covalent bond, atomic orbital overlaps to form a molecular orbital. When orbitals overlap (end-on), we call the bond sigma
bond.
The electron density of each of sigma bond is symmetrical about a line joining the nuclei of the atoms forming the bond.
s-s

p-p

s-p

bond
Bonds formed by (side-way) overlap of p-orbitals are called pi bond.
A pi bond is not symmetrical about the axes joining the nuclei of the atoms forming the bond. Instead, pi bond has two electron clouds, one
arising from each lobe of the p-orbitals
Metallic bonding
In a metal, the atoms are packed closely together in a regular arrangement called a lattice. Metal atoms tend to lose their outer shell electrons and
become positive ions. The outer shell electrons occupy new energy levels and are free to move throughout the metal lattice. The strength of
metallic bonding increases with
1.
2.
3.

Intermolecular forces

Type of bond
Ionic bonding
O-H covalent bond
Hydrogen bonding
Permanent dipole forces
Van der waals forces

Bond strength/kJ mol-1


760
464
20-50
5-20
1-20

Van der waals (dispersion forces/temporary dipole forces)

Permanent dipole forces


Hydrogen bonding

Draw dot-and-cross diagrams to describe the covalent bonding in the following molecules, showing only the outer electron shells.
(a) Carbon monoxide, CO (1 dative bond)
[1]

[5]

(b) Ethyne, C2H2

[1]

(c) Hydrazine, N2H4


(d) Cyanide ion, CN

[1]

(e) Hydroxide ion, OH

[1]

(f) Phosphonium ion, PH4+

[1]

(g) Iodine (II) chloride cation, ICl2+

[1

The boiling points of some Group V hydrides are shown below.

Hydride
Boiling point / C

NH3
33

PH3
88

AsH3
55

SbH3
17

(a) Describe and explain the general trend in the boiling points of the
hydrides from PH3 to SbH3.

[3]

(b) Explain why the boiling point of ammonia, NH3, is higher than that of
phosphine, PH3.

[2]

Ethanol, C2H5OH, is a hydrogen-bonded molecule at room temperature.


(a) What are the requirements for hydrogen bonding to occur between two molecules?

[4]

(b) Draw two molecules of ethanol to show the hydrogen bonding between
them. Include on your diagram any relevant lone pairs of electrons that
play a part in the hydrogen bonding.

[3]

(c) Explain why butane, CH3CH2CH2CH3, has a higher boiling point than 2methylpropane, CH3CH(CH3)CH3, even though they have the same number of
electrons.

[7]

Use ideas about structure, electronegativity and intermolecular forces to explain why phosphorus trichloride, PCl3, is a liquid at room temperature
but phosphine, PH3, is a gas.
Electronegativity values: Cl = 3.0; H = 2.1; P = 2.1

The table lists some properties of nitrogen, oxygen and nitrogen monoxide.

(a) Explain why nitrogen and oxygen have similar boiling points.
(b) Explain why the boiling point of nitrogen monoxide is significantly higher
than those of nitrogen and oxygen.
(c) Explain why the solubility of nitrogen monoxide is significantly higher

than those of nitrogen and oxygen.

Giant covalent
Diamond

Graphite
Silicon (IV) oxide or silicon dioxide
Chapter 4: States of matter
Assumptions of kinetic theory of gases
1.
2.
3.
4.
5.
A theoretical gas that fits this description is called an ideal gas. In reality, the gases we encounter do not fit this description exactly, although they may
come very close. The gases we encounter are called real gas.
Ideal gases
Boyles Law
The volume that a gas occupies depends on
(a) pressure (Boyles Law)
(b) temperature (Pressure Law)
An ideal gas will have a volume that varies exactly in proportion to its Pressure Law
temperature and in inverse proportion to its pressure

Real gases

Do not obey the kinetic theory in two ways:


1.
2.
These differences are especially noticeable at very
1.
2.
Under these conditions,
1. the molecules are close to each other, there are intermolecular forces
between molecules.
2. the volume of the molecules is not negligible compared with the
volume of the container.
Ideal gas equation
PV = nRT
Further application of ideal gas equation

(a) Under what conditions do the properties of an ideal gas differ from
those of a real gas?
[2]
(b) For the conditions you stated in part a, explain how an ideal gas
would behave.
[4]
(c) Explain why the properties of ideal gases differ from those of real
gases.

The relative molecular mass of a volatile liquid can be found by vaporising


the liquid in a gas syringe. 0.0750g of a hydrocarbon vapour occupies
25.0cm3 at 77.0C. Atmospheric pressure is 101.3kPa.
Use the general gas equation to calculate the relative molecular mass of the
hydrocarbon.

A hydrocarbon with relative molecular mass 58.0 exists as a vapour at


100C and atmospheric pressure 101kPa. Under these conditions,
0.100g of this hydrocarbon was present as vapour.
(a) Calculate the number of moles of the hydrocarbon. Give your
answer to 3 significant figures. [1]
(b) What volume, in cm3, does this hydrocarbon occupy under these
conditions?
[4]

Dry air is a mixture whose composition can be considered to be 78.08%


nitrogen, 20.95% oxygen and 0.93% argon by volume.
(a) The density of dry air at R.T.P. is 1.18g/L. Calculate the mass of 24L of this
air.
(b) Calculate the average molecular weight of air particles.

(a) Why is graphite used in making shafts for squash racquets?


(b) Why have graphite fishing rods sometimes proved to be
dangerous accessories?

(a) Explain why graphite is soft and slippery whilst diamond is the hardest
natural substance.
(b) Give one use each for graphite and diamond which depends on these
properties, and explain why it has this use.

[3]

A diagram of the structure of the metal sodium is shown below.

(a) Draw a diagram showing the particles in aluminium.


(b) Use the diagram to explain why the melting point of sodium is less than that
of aluminium.
(c) Potassium is a better electrical conductor than sodium. Explain why.

Using the diagram above, explain why metals are:


(a) good conductors of electricity
(b) malleable and ductile.

Chapter 5: Chemical Energetics


Exothermic

Endothermic

Standard enthalpy change of formation

Standard enthalpy change of combustion

Standard enthalpy change of neutralization

Standard enthalpy change of solution

Standard enthalpy change of atomization

Calculate enthalpy change of reaction from enthalpy changes of


formation

Calculate enthalpy change of reaction from enthalpy changes of


combustion

Propane is a hydrocarbon that has uses as a fuel.


(a) Write the equation for the formation of propane from its elements.
(b) Using the data in the table, calculate a value for the enthalpy change
of combustion of propane:
C3H8 + 5O2 3CO2 + 4H2O

Use the standard enthalpies of combustion in the table to calculate a value for
the enthalpy change of this reaction:
C6H5OH + 3H2 C6H11OH
Compound
C6H5OH
H2
Compound
C6H11OH

Hco / kJ mol1
3064
286
o

H
f / kJ mol
3727
1

C3H8
CO2
H2O

Calculate enthalpy change of reaction using bond energies


The equation below shows the combustion of hydrazine.
N2H4 (l) + O2 (g) N2 (g) + H2O (l)
(a) Copy and balance the equation. [1]
(b) Use bond energies to calculate the enthalpy change for the reaction.
(c) Give three reasons why hydrazine is a good fuel.

105
394
286

Calculate enthalpy change of reaction from Hess Diagram


Given the enthalpy changes H1 and H2 below, construct an enthalpy cycle
that will enable you to find the enthalpy change for the following reaction:
CaCO3 (s) Ca O(s) + CO2 (g)
Hr
CaCO3 (s) + 2HCl (aq) CaCl2(aq) + CO2 (g) + H2O (l) H1
CaO (s) + 2HCl (aq) H2O (l) + CaCl2 (aq)
H2

Given the enthalpy changes H3 and H4 below, construct an enthalpy


cycle that will enable you to find the enthalpy change for the following
reaction:
CuBr2 (s) + 4H2O (l) CuBr2.4H2O (s)
Hr
CuBr2 (s) + aq CuBr2 (aq)
CuBr2.4H2O (s) + aq CuBr2 (aq)

H3
H4

Calculate H for CH4 (g) + NH3 (g) HCN (g) + 3H2 (g), using:
N2 (g) + 3H2 (g) 2NH3 (g)
H = -92kJ
C (s) + 2H2 (g) CH4 (g)
H = -75kJ
H2 (g) + 2C (s) + N2 (g) 2HCN (g)H = +270kJ

Given the enthalpy changes H5 and H6 below, construct an enthalpy cycle


that will enable you to find the enthalpy change for the following reaction:
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)
Hr
HCl (aq) + NaHCO3 (s) NaCl (aq) + CO2 (g) + H2O (l)
2HCl (aq) + Na2CO3 (s) 2NaCl (aq) + CO2 (g) + H2O (l)

H5
H6

Calculate the standard enthalpy change in kJ for the following reaction of


nitrogen dioxide with water:
3NO2 (g) + H2O (l) 2HNO3 (aq) + NO (g)
2NO (g) + O2 (g) 2NO2 (g)
2N2 (g) + 5O2 (g) + 2H2O (l) 4HNO3 (aq)
N2 (g) + O2 (g) 2NO (g)

H = -114kJ
H = -255kJ
H = +181kJ

A spirit burner containing ethanol is used to heat up 200 cm3 of water in a


copper calorimeter.

The apparatus shown on the right was used to measure the enthalpy change
of the reaction
NiSO4 (aq) + Zn (s) Ni (s) + ZnSO4 (aq)

(a) Calculate the enthalpy change of combustion of ethanol using the


information below.
initial temperature of water = 18C
highest temperature of water reached = 45C
initial mass of spirit burner + ethanol = 196.6g
final mass of spirit burner + ethanol = 195.5g
molar mass of ethanol = 46g mol1
[5]
(b) Why is the value of the enthalpy change of combustion in this
experiment so different from the data book value (Hc =
1367kJ mol1)? [2]
(a) Describe how you would use this apparatus to carry out an experiment to
obtain data to calculate the enthalpy change of this reaction.
(b) The results of the experiment are as follows:
volume of NiSO4 solution = 100cm3
initial temperature of NiSO4 solution = 19.5C
final temperature of NiSO4 solution = 23.5C
Use these results to calculate the enthalpy change of the reaction.
(c) What assumptions have been made when calculating the enthalpy change of

this reaction?
(d) What advantages are there of using the apparatus shown above to carry out
the reaction, rather than a glass beaker. Give reasons for your answer.

Chapter 6: Electrochemistry
Oxidation

Reduction

Oxidation number rules

Example

1. The oxidation number of any uncombined element is zero.


2. Group 1 = +1
Group 2 = +2
F = -1
H = +1 (except in metal hydrides, -1)
O = -2 (except in hydrogen peroxides, -1)

3. The oxidation number in an ion is always equal to its charge.


4. The sum of oxidation number in a compound is zero.
In the industrial production of sulfuric acid the following changes take place
to the sulfur:
stage 1

stage 2

stage 3

S
SO2
SO3
H2SO4
(a) For each molecule, give the oxidation number of sulfur.
(b) For stages 2 and 3, state what type of reaction has taken place and explain
your answer.
(c) The equation below describes the reaction of concentrated sulfuric acid
with hydrogen sulfide.
H2S + H2SO4 2H2O + SO2 + S
Use oxidation numbers to explain which species are oxidised and which
are reduced in this reaction.
Electrolysis of brine

In the reactions below, give the oxidation states (oxidation numbers) of


each element indicated in the brackets as a reactant and as a product, and
state whether it has been oxidised or reduced.
(a) CO2 + 2Mg 2MgO + C
(Mg and C)
(b) CaCO3 CaO + CO2
(Ca and O)
(c) 2NO2 N2O4
(N)

Electrolysis of bauxite

Chapter 7: Equilibria
Characteristic of equilibrium
1.
2.
3.

4.
Le Chateliers principle
If a dynamic equilibrium is disturbed by changes in concentration, temperature or pressure (when any of the reactants or products are gases), the position of
equilibrium will shift in the direction that opposes the change.
Kp/Kc expression provides information on quantities of reactants and products at equilibrium.
Kc applies for l, aq and g states.
Kp only applies to g state.
(a) What are the characteristics of an equilibrium reaction? [4]
(b) A mixture of hydrogen and iodine is placed in a closed container at
500C. They react and eventually reach an equilibrium described by
this equation:
H2 (g) + I2 (g) 2HI (g)
Draw a sketch graph to show how the concentrations of hydrogen,
iodine and hydrogen iodide change with time. Label each line clearly.

The equilibrium between four substances, W, X, Y and Z, is shown below:


2W (g) + X (g) Y (g) + Z (g)
In a reaction vessel of 0.5dm3 capacity, a starting mixture of 2mol of W and
3mol of X produced 0.5mol of Y.
(a) Calculate the numbers of moles of W, X and Z at equilibrium.
(b) Calculate the value of Kc and give the units.

Hydrogen reacts with gaseous sulfur, S2, to form hydrogen sulfide:


2H2 ]=]=(g) + S2 (g) 2H2S (g)
At equilibrium, the partial pressures of these gases are H2 (g) = 44kPa, S2
(g) = 0.00040kPa, H2S (g) = 88kPa.
(a) What is the total pressure exerted by this mixture of gases?
[1]
(b) Why can the partial pressure of gaseous sulfur be ignored when
calculating the total pressure in part a? [1]
(c) Calculate the value of Kp for this reaction, expressing partial pressures in
Pa. State the units of Kp.

A scientist studied the equilibrium between gaseous dinitrogen tetroxide,


N2O4, and nitrogen dioxide, NO2, at 298K and 40kPa pressure.
N2O4 (g) 2NO2 (g)
At the start of the experiment, 12.50 103 mol of N2O4 was placed in a
sealed tube. The contents of the tube were then allowed to reach
equilibrium. The number of moles of NO2 at equilibrium was 9.00x10-3mol.
Calculate the value of the equilibrium constant, Kp, for this reaction, stating
the units.

The reaction

The equations for two equilibrium reactions involving NO2 are shown below:
N2 (g) + 2O2 (g) 2NO2 (g)
Hr = +66.4kJ mol1
N2O4 (g) 2NO2 (g)
Hr = +58kJ mol1
(a) What conditions of temperature and pressure favour the formation of NO2
from N2 and O2? Explain your answers using Le Chateliers principle.
(b) At 22C NO2 is a dark brown gas and N2O4 is a light yellow-brown gas.
What would you observe when an equilibrium mixture of NO2 and N2O4 is
compressed at 22C? Explain your answer.

2SO2 (g) + O2 (g) 2SO3 (g)


reaches dynamic equilibrium. The forward reaction is exothermic. The
reaction is catalysed by V2O5. You are given a vessel containing all three
gases at equilibrium.
What will happen to the position of equilibrium if:
(a) you add more oxygen to the vessel?
(b) you remove some sulfur trioxide from the vessel?
(c) the pressure in the vessel is lowered?

(d) more V2O5 is added?


(e) the temperature in the vessel is increased?
(c) Experiments showed that, if 1 mol of N2O4 (g) is allowed to come to
equilibrium with NO2 under standard conditions, only 20% of the N2O4 (g) is
converted to NO2 (g).
Calculate Kc for the reaction. Assume that the volume of the reaction mixture
is 1dm3.
(d) Explain the effect on Kc of an increase in:
(i) pressure

(ii) temperature.

(a) State the BrnstedLowry theory of acids and bases.


[4]
(b) Copy the following equations.
Ring the acid and underline the base on the left-hand side of each
equilibrium.
Identify the conjugate acid and conjugate base on the right-hand side
of each equilibrium.
H2SO4 + HNO3 HSO4 + H2NO3+

(a) What is meant by the term acid?


Give one example to illustrate your answer, including an equation.
(b) Why do all acids have similar properties?
Give an example of a reaction that illustrates that all acids have similar
properties.
(c) Give the observations that would be made in your chosen reaction.
(d) Write a balanced equation for the reaction.

HCl + HI

H2Cl+ + I

HClO4 + CH3COOH

ClO4 + CH3COOH2+

(a) What is meant by the term base? [1]


(b) What is different about alkalis compared with other bases?
[1]
(c) What ion is released by all alkalis?
[1]
(d) Why do alkalis show similar reactions? [2]
(e) Use the reaction with hydrochloric acid to show that two different
alkalis undergo similar reactions. [2]
(f) What is the name given to this type of reaction? [1]
(g) Give the ionic equation for the reaction.

Chapter 8: Reaction Kinetics


Maxwell Boltzmann Distribution Plot

Rate of reaction increased when temperature increased

Rate of reaction increased in the presence of catalyzed