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Physical Chemistry Revision 1 Pg17

Reaction Kinetics
Know the definitions of the following:
Term Definition
rate of The change in concentration of a
rxn reactant or product with time.
i.e. rate at a given time t
= d [reacdt tan t ] = d[ product
dt
]
.
rate The rate equation or rate law is a
eqn mathematical equation that shows
how the rate of reaction is dependent
on the concentrations of the
reactants; it relates the rate of the
reaction to the concentration of
reactants raised to the appropriate
power. E.g. rate = k[A]m[B]n
order  The order of reaction with respect
of to a reactant is the power to which
reactio the concentration of that reactant is
n raised to in the rate law.
(must  The overall order of reaction is the
give sum of the powers to which the
both  concentrations of the reactants are
& raised to in the rate law.
rate The rate constant, k is a
consta proportionality constant in the rate
nt equation of the reaction.
half-life The time required for the
of a rxn concentration of a limiting reactant to
decrease to half of its initial
concentration.
rate- The slowest step in the sequence of
determi steps leading to the formation of the
ning product.
step
activati The minimum amount of energy that
on the reactant particles must possess
energy, before they can collide successfully
Ea to form products
(Two criteria:

catalyst A substance which increases the


rate of a chemical reaction without
itself undergoing any permanent
chemical change. It is regenerated
at the end of the reaction.
Interpretation of the Rate rate
second
Equation first
k zero
order

Consider the following [reactant]

reaction:
A + B C + D
in which the rate equation is given by:
rate = k [A]m [B]n

Determining orders of reaction and rate


equations
(i) Observing initial rates data (Direct
comparison)

(ii) Mathematical equations (Indices


method)

(iii) Graphical data


Question 1
Hydrogen peroxide reacts with iodide ions in acidic
solution as shown below.
H2O2(aq) + 2H+(aq) + 2I(aq)
2H2O(l) + I2(aq)

In a series of experiments, the reaction was carried


out with different concentrations of the 3 reagents
and the following results were obtained.

Expt [H2O2] [H+] [I ] Relative


No. / mol / mol / mol initial rate
dm-3 dm-3 dm-3 / mol dm-3 s-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

(ai) Use the data to deduce the order of reaction


with respect to each reagent. Explain your answers
and write a rate equation.

Solution:

From experiments 2 and 3, [H2O2] and [H+] =


constant.
When [I] increases by 1.2 times, rate
increases by 1.2 times. Therefore, Rate [I ].
Reaction is first order with respect to I .

From experiments 1 and 3, [H2O2] and [I] =


constant.
When [H+] increases by 1.2 times, rate
remains the same.
Reaction is zero order with respect to H+.

From experiments 2 and 4, [H+] and [I] =


constant.
When [H2O2] increases by 1.25 times, rate
increases by ~1.25 (1.024/0.833 = 1.23)
times. Therefore, Rate [H2O2].
Reaction is first order with respect to H2O2.

rate = k [H2O2] [I ]

Alternative approach
(aii)
Two different mechanisms have been
suggested for this reaction.

Mechanism A:
H2O2 + I H2O + IO(Step 1-slow)
H+ + IO HIO (Step 2)
HIO + H+ + I H2O + I2 (Step 3)

Mechanism B:
H2O2 + I + H+ H2O + HIO(Step 1-slow)
HIO + I I2 + OH (Step 2)
OH + H+ H2O (Step 3)

Which mechanism is consistent with your rate


equation in a(i)? Explain your answer.
Syllabus requires you to be able to verify that
a suggested reaction mechanism is
consistent with the observed kinetics.

Solution:

Mechanism A because it has a slow step


(Step 1) involving one molecule of H2O2 and
one I ion.
(b) The decomposition of hydrogen peroxide is a
first order reaction.

H2O2 H2O + O2 H = 98 kJ mol1

The uncatalysed reaction has an activation energy


of 79 kJ mol1.

(bi) Use the data provided to sketch a fully labeled


reaction pathway diagram showing all relevant
energy changes.

Energy Transition State

79 kJ mol-1

H2O2 98 kJ mol-1

H2O + O2

Progress of reaction

(bii) Define the terms activation energy and rate


constant.

Activation energy (Ea) is the minimum


amount of energy that reactants must
possess before a reaction can occur.

Consider the rate equation, Rate = k [A][B]


Rate constant is the proportionality constant,
k, in the experimentally determined rate
equation.

(biii) How will the activation energy and the rate


constant for the reaction be affected by an increase
in temperature? Explain your answer with the aid of
the Boltzmann Distribution diagram if necessary.
When temperature increases,
activation energy remains constant/unaffected,
rate constant increases.
Activation energy of a reaction depends on
the reaction pathway.

When temperature increases, the number of


molecules with energy activation energy
increases.
Therefore, frequency of effective collisions
between molecules with energy activation
energy increases and hence, rate constant
increases.
T1
Fraction of molecules

T2 > T1
No. of molecules with energy Ea at T2
T2
No. of molecules with energy Ea at T1

0
Ea energy
Additional Question:
The diagram shows the Boltzmann distribution
of the speeds of the molecules of a gas. Point
X represents the most probable speed.

If the gas is cooled, in which direction does X


move?

(ii) Graphical Method - reactant-time graph


Expt [H2O2] / mol dm-3 Initial [OH] / moldm-3
1 0.1 0.1
[H2O2] mol dm 3
2 0.1 0.05
0.100

Solution
0.050 Expt 2  To find order of reaction with
0.025 respect to H2O2, use one of the
0.020
Expt I graphs and find the half life. If
0 t/ min
1 2 3 4 5 6 half life is constant, order is 1 wrt
H2O2.
 To find order of reaction with
respect to OH, draw a tangent
at t = 0 for both expts and
compare the value of the
gradient (which represents rate)
when [OH] in expt 2 is half that
in expt 1. If grad of curve from
Question 2
Dinitrogen oxide, N2O, is used as an anesthetic. It
decomposes when heated as follows.

N2O (g) N2 (g) + O2 (g)

The rate of decomposition of pure dinitrogen oxide


may be followed by measuring the total pressure of
the system. In an experiment conducted at 1000K,
in the presence of a gold surface, the total pressure
PT increased as follows :

PT / 25.0 27.5 30.0 32.5 34.0 35.0


kPa
Time / s 0 100 230 420 590 740
PN2O / 25.0 20.0 * 10.0 * 5.0
kPa

(ai) Calculate the partial pressures of N2O ( PN2O )


at 230 s and 590 s.

N2O (g) N2 (g) + O2 (g)


Initial P/kPa 25.0 0 0
Change /kPa -x +x +x
Final P / kPa 25.0-x x x
PT = (25.0 - x + x + x)
= (25.0 + x)
x = 2(PT - 25.0)
( where x = amt of N2O decomposed at any
given time )
PN2O = 25.0 - x = 75.0 - 2PT

At 230 s, PT = 30.0, PN2O = 15.0 kPa


At 590 s, PT = 34.0, PN2O = 7.0 kPa

(aii) By using a graphical method, determine the


order of the reaction with respect to N2O.

Since 1st t1/2 = 2nd t1/2 = 320 s, t1/2 is constant.


Hence order of the reaction with respect to
N2O = 1.
(aiii) Estimate how many half lives would have
elapsed for the partial pressure of N2 to increase to
about 18.8 kPa.

At any time , PN2 = x = 2(PT - 25.0) =


25.0 - PN2O 1m
No. of half- 0 1 2
lives
PN2O / kPa 25.0 12.5 6.25
PN2 / kPa 0 12.5 18.75
Ans : 2 half lives

Additional Question:

If the rate of decay of a radioactive isotope


decreases from 200 counts per minute to 25
counts per minute after 24 hours, what is its
half-life?

A 3 hours D 8 hours
B 4 hours E 12 hours
C 6 hours N89/III/8

Ans: D

No of half-lives: (25/200) = ()n


Graphical method product-time graph

[product]/mol dm-3
Co
7
Co
8
3
Co
4

1
2
Co t1 = t2 = t3
i.e. t 1 is constant
2

0
time/s
t1 t2 t3

 To find order of reaction using product-time


graph,
It is essential to determine value of Co (i.e.
maximum concentration of product formed
upon completion reaction)
 From the graph, time taken for [product] to
increase from 0 to Co = t1
time taken for [product] to increase from Co
to Co = t2
 If t1 = t2 = __ s (always indicate the value
determined from graph in your
presentation), then t1/2 is constant.
Since t1/2 is constant, the reaction is first-
order with respect to the reactant.
Question 3
Carbon dioxide gas is produced when aqueous
bromine reacts with methanoic acid, as shown in
the equation below.
Br2(aq) + HCOOH(aq) 2Br(aq) + 2H+(aq) +
CO2(g)

An experiment was conducted to determine the


order of reaction with respect to bromine. 20 cm3 of
0.50 mol dm-3 of aqueous bromine was reacted with
20 cm3 of 5 mol dm-3 methanoic acid. The volumes
of carbon dioxide gas produced at various times in
the reaction is shown in Table 1.

Time Volume of
/s CO2 / cm3
0 0
30 24.00
60 45.60
90 64.80
120 81.60
180 112.80
240 134.40
360 170.40
480 194.40
600 208.80
Table 1
All volumes are measured at room temperature and
pressure.

(ai) Determine the maximum volume of CO2 which


can be produced from the experiment.

Amt of CO2 = =0.01 mol


volume = 0.01 24 = 0.24 dm3 = 240 cm3

(aii) Plot a graph of volume of CO2 produced


against time.
250
240
230
220
210
200
190
180
170
160
volume of CO2 / cm3

150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600 630
time / s

A second set of experiment was conducted with


the concentration of Br2(aq) kept constant at 0.50
mol dm-3 and the concentration of HCOOH(aq)
varied. The following results were obtained.
initial rate of
Expt initial [HCOOH]
production of
no. / mol dm-3
CO2 / cm3 s-1
1 5.0 0.825
2 1.25 0.206
Table 2

(aiii) Using your graph, together with the results in


Table 2, deduce the order of reaction with respect
to:
1. Br2
2. HCOOH
half-lives are constant at 200 s
1st order w.r.t. Br2

Comparing expt 1 and 2, when [HCOOH]


decreases by 4 times, rate decreases by 4
times
1st order w.r.t. HCOOH
(aiv) Experiment 1 was repeated using 0.40 mol
dm-3 Br2(aq) instead of 0.50 mol dm-3. The
concentration of HCOOH was kept constant at 5
mol dm-3.
Sketch, on the same axes as (ii), the graph of the
volume of carbon dioxide gas produced against
time for this experiment.

Max amt of CO2 = = 0.008 mol


3
Max vol = 192 cm (graph should not exceed
this value)
half-lives = 200 s
mark 2 co-ordinate points (200, 96) and (400,
144) on graph
250
240
230
220
210
200
190
180
170
160
volume of CO2 / cm3

150
140 a(iv)
130
120
110
100
90
80
70
60
50
40
30
20
10
0
0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480 510 540 570 600 630
time / s

(av) The above reaction is catalysed by acid. With


the aid of a well-labelled diagram of a Boltzmann
Distribution curve, explain how the rate of reaction
will be affected by the catalyst.
Catalyst lowers the activation energy by
providing an alternative pathway with a
lower activation energy.
Greater number of particles with energy
higher or equal to activation energy.
Frequency of effective collision increases.
Rate of reaction increases.
Presence of Catalyst
number of
particles
with a given
energy

E'a Ea kinetic energy


Number of particles with energy not less than Ea

Number of particles with energy not less than E'a

Additional Question
The kinetics of the acidcatalysed reaction of
propanone with iodine
CH3COCH3(aq) + I2(aq)
CH2ICOCH3(aq) + HI(aq)
can be investigated experimentally by varying the
concentrations of the three substances involved.
The following results were obtained in an
experiment.
Question 4
Samples of 2-bromo-2-methylpropane were
dissolved in dilute aqueous ethanol (80% ethanol
and 20% water by volume) and reacted with sodium
hydroxide solution. Several experiments were
carried out at constant temperature. The initial rate
of reaction was determined in each case.

Expt [(CH3)3CBr] [OH-] Rate


/ mol dm-3 / mol / mol
dm-3 dm-3 s-1
1 0.020 0.010 20.2
2 0.020 0.020 20.2
3 0.040 0.030 40.4

(a) Calculate a value for the rate constant. Hence


write the rate equation for the reaction.

Compare Expt 1 and 2,


Keeping [(CH3)3CBr] constant, but double
[OH], rate was constant.
Order of reaction wrt to [OH ] is ZERO.
Compare Expt 1 and 3,
Triple [OH ] will not affect rate. But double
[(CH3)3CBr] and rate was double.
Order of reaction wrt to [(CH3)3CBr] is ONE.

Rate = k [(CH3)3CBr]
From Expt 1 data, 20.2 = k (0.020)
k = 1010 s-1

Rate = 1010 [(CH3)3CBr]

The hydrolysis of 2-bromopropane is now


investigated. Samples were dissolved in dilute
aqueous ethanol (80% ethanol and 20% water by
volume) and reacted with sodium hydroxide
solution. The rate equation is found to be as follows:

Rate = 0.24 x 10-5 [CH(CH3)2Br] +


4.7 x 10-5 [CH(CH3)2Br] [OH ]
(bi) The rate equation obtained indicates that the
hydrolysis of 2-bromopropane exhibits a mixture of
both first order and second order kinetics. Suggest
why this may be so.

2-bromopropane is a 2 alkyl halide. It poses


some steric hindrance for the nucleophile to
approach bromoethane compared with a 1o
RX, if the reaction were to proceed by SN2.

On the other hand, if it were to proceed by SN1,


2o carbocation is not as stable compared
with a 3 alkyl halide.
As a result, 2-bromopropane undergoes both
SN1 and SN2 reaction pathways,
simultaneously.
(bii) By deriving an expression in terms of [OH-],
-
4.7[OH ]
show that the % rate due to SN2 is 4.7[OH ] + 0.24
X 100% . -

SN 2
%SN 2 = x 100%
SN 1 + SN 2

4.7 x 10-5 [CH(CH3 )2Br] [OH ]


= x 100%
0.24 x 10 [CH(CH3 )2Br] + 4.7 x 10-5 [CH(CH3 )2Br] [OH ]
-5

4.7[OH ]
= = X 100%
4.7[OH ] + 0.24

(biii) Using the expression derived from (b)(ii),


calculate the % rate due to SN2 for various [OH] of
0.01M, 0.1M and 1.0M.

At [OH ] = 0.01M, % rate = 16.4%


At [OH ] = 0.1M, % rate = 66.2%
At [OH ] = 1M, % rate = 95.1%

(biv) In light of your answer to (b)(iii), state how


the % rate due to SN2 depends on the
concentration of [OH] and explain why it varies in
that manner.

As [OH ] increases, SN2 is favoured and %


rate due to SN2 increases.
SN2 is favoured by strong nucleophile in
high concentration, whereas SN1 is
independent of the type or concentration of
the nucleophile.

(bv) By comparing the magnitude of the two rate


constants in the rate equation given in (b),
comment on the ease of hydrolysis by the two
different pathways.
The Arrhenius Equation is given as follows:
k = A eEa / RT
SN2 component is characterized by a larger
rate constant than the SN1 component.

At the same temperature, a larger rate


constant means a smaller Ea value. For this
reaction, SN2 has a smaller Ea value than
SN1. Hence reaction proceeds via SN2 more
than SN1.

(bvi) Draw a labelled Maxwell-Boltzmann Curve for


this reaction to illustrate the distribution of energy.
Based on your answer to (b)(v), indicate the
activation energies clearly on the diagram for the
two different reaction pathways.
Ea,SN2 < Ea,SN1 : [1m]
Legend and Axis Labels: [1m]
Shape of Curve: [1m]

(bvii)On the same axes, draw the energy profile


illustrating both the SN1 kinetics and the SN2
kinetics components observed for this reaction.
Indicate the activation energies clearly on the
diagram, for the two reaction pathways.


Ea,SN2 < Ea,SN1 : [1m]
Shape of Curve, Axis Labels : [1m]
(bviii) Explain how the rate constant will change if
CH(CH3)2Cl is used instead of CH(CH3)2Br.

As CCl bond is stronger than CBr, it is


harder for the CCl bond to break. Since
reaction involves breaking the C-Hal bond, the
activation energies for forming the
carbocation and transition state will be higher
for both SN1 and SN2 pathways. Hence the
rate constant will decrease.

(bix) Draw the structures of two possible organic


by-products that may be formed in this reaction,
other than CH(CH3)2(OH). Briefly account for their
formations.
O CH2 CH3
H3C C CH3 H2C C CH3
H H

Acid base reaction between ethanol and


NaOH leads to the formation of a small
amount of C2H5O which competes with
OH as a nucleophile.
The presence of strong base also bring
elimination to form alkene.
Pseudoorder reactions.
Consider a reaction in which rate = k[A][B]
If [A] is essentially constant, then rate = k[B]
where k = k[A].

(a) This occurs


(i) when A is present in large excess such
that its concentration hardly changes
(ii) if A is a catalyst.

(b) This is a pseudo first order reaction wrt to A.


If a graph of [B] against time was plotted,
(i) the graph will have a constant half life
(t1/2)
(ii) t1/2= ln2/k = ln2/(k[A]). The true rate
constant k can be found.

6. Catalysis

Two modes of catalysis:


(a) Homogeneous (catalyst and reactants are in
the same phase)
(b) Heterogeneous (catalyst and reactants are
in different phase)

(a) Heterogeneous catalysis

(i) Important steps in heterogeneous catalysis


Step 1 Adsorption of the reactant particles
onto the active sites on the surface
of the catalyst.
- Weak bonds form between the
reactant particles and the catalyst.
- Surface concentration of the
reactants is increased.
Step 2 Reaction at the surface.
- The activation energy of this
process is lower than that of the
uncatalysed reaction because the
bonds within the reactant
particles are weakened by the
adsorption effects, thereby
reducing the energy required to
disrupt them
- The reactant particles are brought
into close contact and are properly
orientated for reaction
Step 3 Desorption of the reactants or
products from the surface.

(ii) Examples of heterogeneous catalysis


Haber Process
N2(g) + 3H2(g) 2NH3(g)
Conditions: 250 atm, 450C, Fe
Catalytic converter
As the gases enter, the oxides of nitrogen
(NO and NO2) are reduced to N2 by the excess
CO present, with rhodium acting as the catalyst.
Rh
2NO + CO N2 + CO2

The CO is also oxidised to CO2 with platinum


and palladium as the catalysts.
Pt/Pd
O2 + CO CO2

The unburnt hydrocarbons are oxidised to CO2


and H2O with platinum and palladium as the
catalysts.

(b) Homogeneous catalysis

Reaction catalysed by Fe3+:

Step 1: 2I (aq) + 2Fe3+ (aq) I2 (aq) +


2Fe2+ (aq)
catalyst
intermediate

Step 2: 2Fe2+ (aq) + S2O82 (aq) 2SO42


(aq) + 2Fe3+ (aq)
Intermediate
catalyst regenerated

The catalysed reaction proceeds via a 2-step


route. Each step involves a reaction between
oppositely charged ions which have a natural
tendency to attract each other. This lowers the
activation energy and enhances the reaction
rate. (Ecell > 0 for each step of the reaction)

Enzymes catalyse reactions by providing an


alternative reaction pathway with a lower
activation energy. To bring this about, the
enzyme forms a complex with the substrate or
substrates (reactants) of the reaction. Thus a
simple picture of the enzyme action is:

substrate + enzyme enzyme/substrate


complex enzyme + products

Once the products of the reaction are formed,


they are released and the enzyme is free to form
a new complex with more substrate.
Extra:

Graphs of reaction rate against temperature for different


types of reactions
reaction rate reaction rate reaction rate

temperature temperature temperature

(a) for most reactions (b) explosive reactions (c) enzyme-catalysed reactions

Enzymes is a biological catalyst which catalyse


reactions by providing an alternative reaction
pathway with a lower activation energy.
Note:
 Enzymes are highly specific, catalyzing only
one particular type of reaction.
 They are denatured at high temperature.
 Enzyme activity is affected by pH different
enzymes have differing optimum pH levels.
Chemical Energetics Pg 12
Know the definitions of the following:
Symbol 1 mol of Definition
Hro The enthalpy change when molar quantities of reactants as specified by
the chemical equation react to form products at 1 atmosphere pressure
and 298 K temperature.
Hfo pure compound The enthalpy change when 1 mole of a pure compound is formed from its
formed constituent elements in their standard states, at 298 K and 1 atm.
*formation from If it is negative (formation reaction is exothermic), the product is
elements in energetically / thermodynamically more stable than the reactant elements.
standard states. C(s) + 2H2(g) CH4(g)
Hco substance The heat energy evolved (ie exothermic) when 1 mole of the substance is
completely completely burned in oxygen at 298 K and 1 atmosphere pressure.
burned in CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
oxygen
Hhydo gaseous ion The heat energy evolved when 1 mole of the gaseous ion is dissolved in a
dissolved large amount of water at 298 K and 1 atm.
Na+(g) Na+(aq)

Hsolno solute dissolved The heat change when 1 mole of solute is completely dissolved in enough
solvent so that no further heat change takes place on adding more solvent
(infinite dilution) at 298 K and 1 atm.
NaCl(s) + aq Na+(aq) + Cl(aq)
Hneuto water formed The heat change when an amount of acid neutralises a base to form 1
mole of water (in dilute aqueous solution) at 298 K and 1 atmosphere
pressure.
NaOH(aq) + HCl(aq) NaCl (aq) + H2O(l)

Hato gaseous atoms The enthalpy change when 1 mole of atoms in the gas phase is formed
formed from the element in the defined physical state under standard
conditions.C(s) C(g) or Cl2(g) Cl(g)
LE pure ionic Lattice energy is the enthalpy change when one mole of a pure solid ionic
compound compound is formed from its constituent gaseous ions under standard
formed conditions.
Na+(g) + Cl(g) NaCl (s)
BE particular bond The bond energy of a X-Y bond is the average energy absorbed when 1
broken mole of X-Y bonds are broken in gaseous state. The stronger the bond,
the higher the bond energy.
Cl2(g) 2Cl(g)
BDE particular bond Bond Dissociation Energy of a X-Y bond is the energy required to break 1
in a particular mole of that particular X-Y bond in a particular compound in gaseous
compound state.
broken
1st IE gaseous M+ First ionisation energy is the energy required to remove 1 mole of
ions formed electrons from one mole of gaseous atoms in the ground state to form one
from one mole mole of gaseous unipositive charged cations.
of M atoms Na(g) Na+(g) + e
1st EA gaseous X ions First electron affinity is the energy change when 1 mole of electrons are
formed from added to one mole of atoms in the gaseous state to form one mole of
one mole of X gaseous X ions.
atoms Cl(g) + e Cl(g)
Summary of problem solving approach for
Chemical Energetics

(i) q = mcT
(ii) Shortcuts: Use of formulae/ bond energies.
(iii) Hess' Cycle
(iv) Energy Level Diagram

(i) Using q = mcT to find heat energy released/


absorbed.
It is easy to identify when to use this equation.
The question will mention that there is a rise in
temperature in the solution, and immediately
this equation should come to mind. However,
many students do not understand what the
symbols represent.
(c)-Specific heat capacity of water (m) mass
quantity of heat required to raise the temperature of the mass that is computed must be the
1g of water by 1 K. The heat energy released or mass of SOLUTION ONLY (aqueous
absorbed is used to raise or lower the temperature of solutions consist mainly of water) and does
water. The mass is thus mass of SOLUTION ONLY. not include mass of any solids.
It is usually equivalent to volume (cm3) of
solutions, assuming that density of solution
is 1 g cm3

Step 2: Finding enthalpy change of reaction


using H = q/n
Note: n = no. of moles of limiting reagent
Question 1
Chemical companies manufacture containers filled
with liquid butane for use by campers. The enthalpy
change of combustion of butane is 3000 kJ mol1.
(ai)Define the term enthalpy change of
combustion.

(aii) Write an equation for the complete


combustion of butane, C4H10.

The enthalpy change of combustion of a


substance is the heat evolved when one mole
of the substance is completely burnt in
oxygen.
at 298 K and 1 atmosphere pressure
C4H10(g) + 13/2 O2(g) 4CO2(g) + 5H2O(l)

A camper estimates that the liquid butane left in a


container would give 1.2 dm3 of butane gas
(measured at ordinary temperature and pressure).

(bi) Calculate the maximum mass of water at 25 oC


that would be brought to the boiling point by burning
this butane with the aid of additional information
given below.
70% of the heat from the butane is absorbed by
the water,
the specific heat capacity of water is 4.18 J g1 K
1
, and
1 mol of a gas occupies 24 dm3 at ordinary
temperatures and pressures.

Amount of butane = 1.2/24 = 0.050 mol


Heat absorbed by water = (70/100)(Heat released
from combustion of butane)
= (70/100)(0.050)(3000) = 1.05 x 105 J
Let m be the maximum mass of water brought to
boiling.
Heat absorbed by water = mcT
= (m)(4.18)(100 25) = 313.5m J
Therefore, (313.5)(m) = 1.05 x 105 m = 335 g

(bii) Suggest how the camper might have estimated


how much butane was left in the container.
If the mass of the empty container is known, the
mass of butane left may be estimated by weighing.

Question 2
MTBE as well as its isomer MTBE A is added to car
petrol as oxygenates. There has been concern over
the leakage of MTBE and MTBE A into water
supplies, mainly because of the foul taste it gives to
water supplies.

In the manufacture of fuel for industries, liquid


MTBE A is added as a solvent to petroleum to
reduce pollution.
(a) What is meant by the standard enthalpy change
of formation of MTBE A?

Standard enthalpy change of formation of


MTBE A is the energy change when one
mole of MTBE A is formed from its
elements at standard conditions.

(b) Using relevant information from the Data


Booklet and the data provided, obtain a value for
the bond energy for the OH bond in MTBE A, by
means of an appropriate energy cycle. [3]

Data provided: Hat (C) = +715 kJ mol1,


Hf (MTBE A) = 380 kJ mol1
and Hvap (MTBE A) = +50.7 kJ mol1
What is missing in the energy cycle?
State symbols
Balanced equations

By Hess Law,
380 = 5(715) + 6(436) + (496) [4(350) +
11(410) + 360 + BE(OH)] 50.7

BE(OH) = +498 kJ mol1

(c) Suggest a reason for the difference in the OH


bond energy obtained in (b) from the value given in
the Data Booklet.
The bond energy values from the Data Booklet
are average values.

Sometimes you may have to suggest other


reasons. E.g.
Additional Question

The compound furan, (CH)4O, is unsaturated and


has a structure in which the four carbon atoms and
one oxygen atom are connected together in a ring.
It is a liquid at room temperature with a boiling point
of 31oC. It is used to make solvents and nylon.
The displayed formula of furan is as follows:
HCCH
|| ||
HC CH

O
(i) By constructing an appropriate energy cycle,
calculate the enthalpy of the following reaction of
furan at 298K :
(CH)4O (l) 4C (g) + 4H (g) + O (g)
Use the following given enthalpy values:
Hf[(CH)4O] = -62 kJ mol-1
Hat (C) = +717 kJ mol-1
Hat (H) = +218 kJ mol-1
Hat (O) = +250 kJ mol-1
[Ans: Hr = +4052 kJ mol-1]

(ii) It is also possible to calculate the value of the


enthalpy change for the reaction above by using
appropriate bond energy values from the Data
Booklet. The value calculated using this method
differs from that calculated by using the Hess Law
approach in part (ai).
By considering the bonding in furan and the
definition of bond energy, suggest one reason for
the difference in enthalpy values.

Ans:
In a(ii), furan is a liquid at room temperature and
bond energy is applicable for gaseous
molecules
or delocalisation effect in furan is not considered.

(d) In a combustion reaction of industrial fuel,


MTBE is completely combusted in an engine
cylinder at 175 C which had an internal volume of
1055 dm3.

(i) Determine the pressure (in pascals)


exerted by the carbon dioxide emitted by
the combustion of 4 kg of MTBE fuel.

No. of moles of MTBE in 4 kg of fuel =


1000 4
88
= 45.45 mol
C5H12O 5 CO2
227.27 x 8.31 x (175+273)
Pressure of CO2 = 1055 x10-3

= 8.02 105 Pa
(ii) In fact, the pressure inside the engine
cylinder was found to be slightly lower than
the value calculated in d(i). Explain this
discrepancy in values observed.

CO2 is not an ideal gas. There are significant


intermolecular attractions between CO2
molecules.
Pressure observed is hence lower than the
theoretical value.

Question 3
Iron(III) bromide is a fairly strong Lewis acid, and is
used as a catalyst in organic synthesis. Iron(III)
bromide dissolves in water to give a brown, acidic
and corrosive solution.

(a)Define the term standard enthalpy change of


formation with respect to iron(III) bromide.

Fe(s) + 3/2Br2(l) FeBr3(s)


The standard enthalpy of formation is the
change in energy when 1 mole of FeBr3, at its
standard state, is formed from its constituent
elements in their standard states at 1 atm and
298 K.
(b) By using relevant data from the Data Booklet
and the following data, draw an energy level
diagram and calculate the lattice energy of
iron(III) bromide.
First electron affinity of bromine 325 kJ mol1
Enthalpy change of atomisation of bromine + 112 kJ mol1
Enthalpy change of atomisation of iron + 350 kJ mol1
Enthalpy change of formation of iron(III) bromide 320 kJ mol1

Checklist:
Axis with units

By Hess Law,
350 + 3(112) + 762 + 1560 + 2960 + 3(325) +
LE = 320
LE = 5313 kJ mol1
(c) The experimental value for the lattice energy of
iron(III) bromide is found to be 5268 kJ mol1.
Comment on and suggest reasons for the
difference between this value and the value you
obtained in (b).

When there is a large difference in


electronegativity between the ions in a crystal,
as in the case of the alkali metal halides then
the ionic model is satisfactory. However as the
difference in electronegativity gets smaller, as
in the case of the silver halides, the bonding is
different from what the ionic model predicts.
The bonding in this case is not purely ionic
but intermediate in character between ionic
and covalent. The ionic bonds have been
polarised giving some covalent character.
Question 4
Tetraethyl-lead (IV), Pb(C2H5)4, is an example of an
organometallic compound. It can be used as an
antiknock agent in petrol. At the high temperature in
a car engine, the Pb-C bond in Pb(C2H5)4, breaks to
yield lead atoms and ethyl radicals.

(ai) By using the VSEPR theory, predict the shape


of the Pb(C2H5)4 molecule.
Tetrahedral (4 bp & no l lp, equal repulsion
between the 4 bp)

(aii) Using only the data provided below, draw an


energy level diagram to calculate H1, the enthalpy
change of the following reaction:
2C(g) + 5H(g) CH3CH2(g)
Data:
Enthalpy change of atomization of C(s), H2 +717 kJ mol1
Enthalpy change of atomization of H2(g), H3 +218 kJ mol1
Enthalpy change of formation of CH3CH3(g), H4 85 kJ mol1
Bond dissociation energy of the first C-H bond in +435 kJ mol1
CH3CH3(g), H5

Enthalpy/ kJ mol-1
2C(g) + 5H(g) + H(g)

2H2 + 6 H3
H1
CH3CH2(g) + H(g)

0 2C(s) + 3H2(g)

H4 H5

CH3CH3 (g)
By Hesss Law,
H1 = H4 + H5 2H2 6H3
= 435 + (85) 2(717) 6(218)
= 2392 kJ mol-1

(aiii) Hence, with the aid of the data in (ii) and


additional data given below, draw an energy cycle
to calculate the Pb-C bond energy in Pb(C2H5)4.
Data:
Enthalpy change of atomization of Pb(s), H6 +195 kJ mol-1
Enthalpy change of formation of Pb(C2H5)4(g), H7 +264 kJ mol-1

C)
4 BE (Pb
Pb(C2H5)4(g) Pb (g) + 4CH3CH2(g)

H7 4H1

H6+ 8 H2 + 20 H3
Pb(s) + 6C(s) + 10H2(g) Pb(g)+ 8C(g) + 20H(g)

4 BE (PbC) = 4H1 + H6 + 8H2 + 20H3 H7


= 4(2392) + 195 +8(717) + 20(218) 264
= 459 kJ
Mean Pb-C bond energy = 459/4 = 115 kJ mol-1
Question 5
Diamond and graphite are allotropes of carbon.
Using the following data, construct an energy cycle
to calculate the standard enthalpy change of
reaction for the conversion of diamond to graphite.
C(diamond) C(graphite)
Reaction H o / kJ mol1
C(diamond) + O2(g) CO2(g) 395.4
C(graphite) + O2(g) CO(g) 109.0
CO(g) + O2(g) CO2(g) 283.0

By Hess Law,
Hreaction = 395.4 ( 283 109)
= 3.4 kJ mol1

(b) By considering the structures of diamond and


graphite, explain why the entropy change for
the conversion of diamond to graphite is
positive.
RECALL:
Entropy, S, is a measure of the randomness of
matter and energy of a system in a system.
S =Sfinal -Sinitial a measure of dispersal in
energy due to a change in entropy.
Units: J mol1 K1
S >0 system becomes more disorder.

The structure of graphite has more


disorderliness due to the presence of
delocalised electrons between the planes.
Diamond has a giant covalent structure where
the carbon atoms are bonded to each other in
a (regular) tetrahedral manner within the lattice.

Factors affecting entropy are:


change in temperature: temperature
molecules/ions undergo greater vibration( in
solid)
and rapid motion(in liquids & gases); reducing
the orderliness

change in phase (Sgas>>Sliquid>Ssoild)

change in number of particles: S as the no.


of particles (system becomes less orderly.
mixing of particles: orderliness is reduced as
molecules become randomly mixed
(c) Explain why the conversion of diamond to
graphite is spontaneous at all temperatures.

Since S > 0, hence TS is always positive.


G = H TS will always be negative.
Hence, since G < 0 at all temperatures, the
conversion is spontaneous at all temperatures.
RECALL
Effect of temperature on Spontaneity
H S Remarks
- + Rxn is spontaneous at ALL temperature
- - Rxn is spontaneous only at LOW temperature (e.g. condensation, precipitation)
such that H > TS
+ + Rxn is spontaneous only at HIGH temperature (e.g. melting, dissolving)
Such that H < TS
0 + The reduction of Gibbs free energy arises completely due to increase in
randomness of the system.

(d) Using the grid provided below, sketch an energy


profile diagram of this conversion of diamond to
graphite, given the activation energy for the
reaction to be 726 kJ mol1.
Energy

= +726 kJ mol-1

diamond =3.4 kJ mol-1


graphite

Progress of reaction

Chemical Bonding and Gases

Question 1

The relative molecular mass and the boiling point of


methanal, methanol and methanoic acid are given
in the table below.

Compounds Relative Boiling Point /


Molecular Mass C
Methanal 30.0 -21.0
Methanol 32.0 64.7
Methanoic 46.0 100.7
Acid

(a) Explain the differences in their boiling points.


Methanal, methanol and methanoic acid are all
polar molecules and exist as simple
molecular structure.
Methanal has permanent dipole-permanent
dipole interaction between molecules.
Methanol and methanoic acid have hydrogen
bonds between molecules.
Since permanent dipole-permanent dipole is
weaker than hydrogen bonds, less energy is
needed to over the attractions between
methanal. Hence, methanal has the lowest
boiling point.

Methanoic acid forms more extensive


hydrogen bonds than methanol. Thus, more
energy is needed to overcome the attractions
between methanoic acid. Hence, boiling point
of methanoic acid is higher than that of
methanol.
[Generally, compare:
*difference between methanal and methanol
and methanoic acid
*difference between methanol and methanoic
acid]
(b) In benzene solution, the measured relative
molecular mass of methanoic acid is approximately
92.0. Explain the observation and include relevant
diagram in your answer.

In benzene solution, methanoic acid dimerises


through hydrogen bonds.
O Must show lone
HO
CH3 C pairs on O and the
C CH3
OH partial charges!!
O
hydrogen bonds

Question 2
Explain the following observations:
(a) Sulfur has a lower first ionisation energy than
phosphorus.

S [Ne] 3s2 3px2 3py1 3pz1 P [Ne] 3s2 3px1


3py1 3pz1
S has a lower 1st I.E. than P due to the inter-
electronic repulsion between paired
electrons in a 3p orbital of S.

(b) Carbon dioxide and silicon dioxide have


widely different melting points.

CO2 exists as simple molecules with weak


van der Waals forces of attraction between
molecules. SiO2 has a giant molecular
lattice structure with strong covalent bonds
between atoms.
SiO2 has a much higher melting point than
CO2.

(c) 2-Nitrophenol has a lower melting point than


4-nitrophenol.

2-nitrophenol is able to form intra-molecular


hydrogen-bonding between the OH and
NO2 groups. Hence its inter-molecular
hydrogen bonding is less extensive than that
of 4-nitrophenol. Less energy is required to
break the intermolecular forces of attraction
and it has a lower melting point.

Good to include diagram to illustrate the H-


bonding!

(d) The bond angle in PCl3 is larger than that in


AsCl3.

P is more electronegative than As. The bond


pair electrons in PCl3 are closer to the central
P atom as compared to that in AsCl3. There is
more repulsion between the electrons /
greater bond pair-bond pair repulsion and
hence the bond angle increases.
Question 3
(a) Gallium chloride, Ga2Cl6, can be formed by the
reaction between gallium hydride, GaH3 which has
a low boiling point, with anhydrous hydrochloric
acid at -95oC.

(i)Given that gallium chloride has a structure


analogous to that of aluminium chloride, Al2Cl6,
draw a labelled diagram to show the types of
bonding involving the molecules of gallium
chloride in the vapour state.
Cl Cl Cl

Ga Ga

Cl Cl Cl

(ii) Suggest why the pressure of gallium chloride


vapour could increase more rapidly with
temperature than that predicted by the ideal gas
equation.

Dative bonds would break / cleave at high


temperature.
The pressure increases more rapidly due to
dissociation of Ga2Cl6 / dimer to monomer / GaCl3.

(iii) Predict, with reasoning the solubility of gallium


hydride in tetrachloromethane.
GaH3 has a simple molecular structure.
The weak van der Waals forces between the GaH3
molecules is compatible to the weak van der Waals
forces between tetrachloromethane molecules.
Hence, GaH3 is soluble in tetrachloromethane.

(b) A steel target is bombarded with a beam


containing both nitrogen and boron ions. The
nitrogen and boron combine to form boron nitride,
the empirical formula of which is BN. Boron nitride
has a graphite-like structure in which boron and
nitrogen atoms alternate in arrangement. However,
unlike graphite, boron nitride is an electrical
insulator.
(i) Draw a section of the structure of boron nitride,
indicating all the types of bonds involved.
Covalent bonding
B N
Dative bonding
B N B
N B N
B N Weak Van der Waals
N B
N B N Correct sketch showing at
B N B least 3 hexagonal units
(Weak Van der Waals b/w B
N B and B atoms and N and N
atoms [0]

(ii) Predict, with reasoning whether you expect


boron nitride to be volatile. Explain your answer
with reference to the chemical bonding and
structure of boron nitride.

Boron nitride has a giant molecular structure.


Large amount of energy required to overcome the
extensive covalent bonding between atoms in a 3-
dimensional structure.
Boron nitride has a high melting point.
Hence, boron nitride has low volatility or is non-
volatile.

(iii) It is suggested that boron nitride can be made


an electrical conductor by inserting certain atoms
into the structure such as rubidium. This results in
the formation of a solid with enhanced electrical
conductivity.
Explain how the introduction of rubidium into the
boron nitride structure enhances the electrical
conductivity of boron nitride.
Rubidium has a giant metallic structure or Rubidium
is a metal.
Rubidium enhances the electrical conductivity of
boron nitride with its sea of delocalised electrons.

(iv) When heated under high pressure, this form of


boron nitride is converted into another form which is
an extremely hard solid. Suggest one application
for this new form of boron nitride.
It can be used as a cutting tool / drill bit / abrasive
material.
or for drilling
Question 4
(ai) State two assumptions of the kinetic theory of
gases.
negligible intermolecular forces of attraction.
volume of the gas molecules is negligible compared
to the volume it occupies.

(aii) Carbon dioxide is a nonideal gas. The graph


below shows experimental values of compressibility
factor (Z) plot for one mole of carbon dioxide gas.
(Z = pV/RT)
Z = pV/RT

On the plot given, sketch the graph to illustrate the


behavior of an ideal gas.

(aiii)State the type of hybridisation present for the


carbon atom in carbon dioxide molecule.
sp
In the industrial liquefaction of air, highpressure air
is precooled in a coil surrounded by cold water. It
is then allowed to expand into a region of low
pressure, where upon it cools down by a large
amount. An ideal gas does not show this behaviour.

(bi) Suggest why the expansion of air into a region


of low pressure is an endothermic process.

Expansion into low pressure requires the molecules


to overcome intermolecular forces of attraction in
order to move apart.
hence, heat is absorbed by the molecules from the
surroundings, making the gas cool.

(bii) Real gases like carbon dioxide can be liquefied


at room temperature just by pressuring them.
Explain why the application of pressure causes the
gas to liquefy.
When gas is compressed, the molecules are very
close together, and the intermolecular forces of
attraction become significant.

(c) Gases can only be liquefied by pressure alone if


their temperature is below their critical temperature.
Beyond the critical temperature and pressure, the
compound exists as supercritical fluid, a state that
resembles a gas but has density closer to the liquid
phase.
Supercritical carbon dioxide has been widely used
as a solvent for dry cleaning. One way of
overcoming the problem of poor solubility of oils in
carbon dioxide involves the use of surfactants. An
example of such surfactant polymer is shown below.
CH2 CH CH2 CH

m CO
n
OCH2(CF2)6CF3

DeSimones surfactant polymer


(ci) By reference to the type of intermolecular
forces, explain how the use of surfactants like
DeSimones surfactant polymer helps supercritical
carbon dioxide become a more effective dry
cleaning solvent.
The fluorinated alkyl group in the surfactant can
dissolve well in the carbon dioxide solvent (due to
pd-pd between polar ends of CO2 and C-F bond)
while its hydrocarbon chain can interact favourably
with oils (id-id).

Thus the surfactant molecules will help to bind to oil


from clothes and is removed together by carbon
dioxide, making it a good dry cleaning solvent.

(cii) Ammonia is another real gas. Explain how the


critical temperature of ammonia would compare to
that of carbon dioxide.

Ammonia gas has higher critical temperature than


carbon dioxide. Stronger intermolecular forces of
attraction (hydrogen bonding compared to van der
Waals), requires higher temperature to prevent gas
from being liquefied.