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CHEM1001/CHEM1101 combined

2003-N-8

November 2003

You are a member of a research team of industrial chemists who are discussing the
operation of an ammonia plant. Ammonia is formed from nitrogen and hydrogen
according to the following equilibrium reaction.
N2(g) + 3H2(g)

Marks
3

2NH3(g)

The plant operates close to 700 K, at which Kp is 1.00 104 atm2 and employs the
stoichiometric ratio 1:3 of N2:H2. At equilibrium the partial pressure of NH3 is
50 atm. Calculate the partial pressures of each reactant and hence the total pressure
under these conditions.
The equilibrium constant in terms of partial pressures, Kp, is given by:
Kp =

( )

( )( )

If the partial pressure of N2(g) = x, the partial pressure of H2(g) = 3x:


Kp =

()
()()

= 1.00 10-4 or 27x4 =

.
()

= 2.50 107

Hence, x = 31 atm. Therefore, = 31 atm, = 3 31 atm = 93 atm


Ptotal = = (31 + 93 + 50) atm = 174 atm
p(N2) = 31 atm

p(H2) = 93 atm

p(total) = 174 atm

Ammonium carbamate (NH2COONH4) is a salt of carbamic acid that is found in the


blood and urine of mammals. At 250 C, Kc = 1.58 108 M3 for the following
equilibrium:
NH2COONH4(s)
2NH3(g) + CO2(g)
If 7.81 g of NH2COONH4 is introduced into a 0.500 L evacuated container, what is
the total pressure inside the container at equilibrium at 250 C?
If x mol of ammonium carbamate decomposes, it will produce 2x mol of NH3(g)
and x mol of CO2(g). As ammonium carbamate is a solid, it does not appear in the
expression for Kc. Therefore:
Kc = [NH3(g)]2[CO2(g)] = (2x)2(x) = 4x3 = 1.58 10-8
Hence, x = 0.00158 M or
[NH3(g)] = 2 0.00158 = 0.00316 M and [CO2(g)] = 0.00158 M.
ANSWER CONTINUES ON THE NEXT PAGE

The concentration is given by c =


Hence,

. Hence for each component P =

= cRT.

Ptotal = (0.00316 M) RT + (0.00158 M) RT


= ((0.00316 + 0.00158) M) (0.08206 L atm K-1 mol-1) ((250+273) K)
= 0.203 atm

CHEM1001

2004-J-6

June 2004

Briefly describe the following ideas or phenomena.


Dynamic equilibrium
A reaction at equilibrium has not stopped - the rate of the forward reaction is
equal to the rate of the backward reaction - a dynamic situation.

The difference between Q and K


K is the equilibrium constant. For a particular reaction it is dependent on the
temperature only. Q is the reaction quotient. It can be calculated from the
concentrations and pressures of the reactants and products. Q = K when the
reaction is at equilibrium.
If Q < K, the reaction will proceed to the right to produce more product(s).
If Q > K, the reaction will proceed to the left to produce more reactant(s).
Effect of a catalyst on equilibrium
A catalyst lowers the activation energy of a reaction by providing an alternative
reaction pathway or mechanism. It has no effect on the equilibrium position, but
it does allow equilibrium to be established faster.

CHEM1001

2004-J-9

June 2003

A saturated solution of iodine, I2, in water contains 0.330 g I2 per litre, but more than
this amount can dissolve in a KI solution because of the following equilibrium.
I(aq) + I2(aq)

I3(aq)

A solution of KI (0.100 M) dissolves 12.5 g of iodine per litre, most of which is


converted to I3(aq). Assuming that the concentration of I2 in all saturated solutions
is the same, calculate the equilibrium constant for the above reaction.
The molar mass of I2 is (2 126.90) g mol-1 = 253.8 g mol-1. Hence,
number of moles =

.
.

= 0.0013 mol

As this amount dissolves in a litre of water, the concentration of I2 in the


saturated solution of iodine in water is 0.0013 M.
.

Similarly 12.5 g of I2 corresponds to

.
of KI solution, this has a concentration is 0.0493 M.

= 0.0493 mol and in a litre

For the equilibrium, the reaction table is therefore:

[initial]
change
[equilibrium]

I-(aq)
0.100
-x
0.100-x

I3-(aq)
0
+x
x

I2(aq)
0.0493
-x
0.0493-x

Assuming that [I2(aq)] is the same as in the saturated solution (as stated in the
question), 0.0493 x = 0.0013 so x = 0.048 giving:
[I-(aq)] = 0.100 0.048 = 0.052 M, [I2(aq)] = 0.0013 M and [I3-(aq)] = 0.048 M.
The equilibrium constant is therefore:
Kc =

[ ]

[ ]

(.)
. (.)

= 710

Answer: 710

CHEM1001

2005-J-7

June 2005

Aluminium acts as a reducing agent in the thermite reaction where Fe2O3 is reduced to
metallic iron. Write a balanced equation for the thermite reaction.

22/01(a)
Marks
4

2Al(s) + Fe2O3(s) Al2O3(s) + 2Fe(s)


What is the maximum theoretical mass of Fe that can be produced when 270 g of Al
reacts with excess Fe2O3 in the thermite reaction?
270 g of aluminium corresponds to:
number of moles =

mass of Al
270
=
=10. mol
atomic mass of Al 26.98

From the chemical equation, 2 mol of Fe is produced for every 2 mol of Al


consumed. Hence, 10.00 mol of Fe is the maximum yield. This corresponds to:
mass of Fe = number of moles of Fe molar mass of Fe
= 10. g 55.86 g mol-1 = 560 g
Answer: 560 g
What does the superscript o mean in the symbol Hf?

All reactants and products are in their standard states: the most stable form of
the substance at a pressure of 1 atm and a temperature of 298 K.

Briefly describe what is meant by Dynamic Equilibrium?


A reaction at equilibrium has not stopped - the rate of the forward reaction is
equal to the rate of the backward reaction - a dynamic situation.

CHEM1001

2006-J-7

June 2006

Heating SbCl5 causes it to decompose according to the following equation.


SbCl5(g)

SbCl3(g) + Cl2(g)

A sample of 0.50 mol of SbCl5 is placed in a 1.0 L flask and heated to 450 C. When
the system reaches equilibrium there is 0.10 mol of Cl2 present. Calculate the value of
the equilibrium constant, Kc, at 450 C.
One mole of Cl2 is generated by the decomposition of one mole of SbCl5. As 0.10
mol of Cl2 is present at equilibrium, (0.50 0.10) = 0.40 mol of SbCl5 must be left.
One mole of SbCl3 is generated alongside the production of one mole of Cl2 so the
number of moles of SbCl3 = number of moles of Cl2 = 0.10 mol.
number of moles
. The
volume
concentrations are therefore: [SbCl5(g)] = 0.40 M, [Cl2(g)] = [SbCl3(g)] = 0.10 M.

The volume of the flask is 1.0 L so the concentration =

The equilibrium constant in terms of concentrations, Kc, is therefore:


Kc =

[Cl 2 (g)][[SbCl 3 (g)] (0.10)(0.10)


=
= 0.025
[SbCl 5 (g)]
(0.40)
Answer: Kc = 0.025

22/01(a)
4

CHEM1001

2007-J-6

Determine Kc for the reaction

O2(g) + Na2O(s)

Na2O2(s)

Na2O(s)

2Na(s) + O2(g)

Kc = 2 1025 at 25 C.

Na2O2(s)

2Na(s) + O2(g)

Kc = 5 1029 at 25 C.

Data:

June 2007
at 25 C.

The reaction involves the formation of Na2O2(s) from Na2O(s) and thus involves
the first reaction and the reverse of the second reaction. The reactions can be
combined:
Na2O(s)

2Na(s) + O2(s)

2Na(s) + O2(g)

Na2O(s) + O2(g)

Na2O2(s)

Na2O2(g)

Kc = 2 10-25
Kc =

1
= 2 1030
29
(5 10 )

Kc = (2 10-25)

Answer: 4 103

1
= 4 103
29
(5 10 )

22/01(a)
2

CHEM1001

2007-J-9

Kp = 7.0 for the reaction

Br2(g) + Cl2(g)

June 2007
2BrCl(g)

at 400 K.

Suppose a 1.0 L flask is filled with 0.30 atm Br2(g) and 0.30 atm Cl2(g) at 400 K.
Find the pressures of all three gases at equilibrium.
The equilibrium constant in terms of partial pressures, Kp, is given by:
Kp =

(PBrCl )2
(PBr2 )(PCl2 )

The reaction table is:


pressure

Br2(g)

Cl2(g)

2BrCl(g)

start

0.30

0.30

change

-x

-x

+2x

equilibrium

0.30-x

0.30-x

2x

The equilibrium constant in terms of partial pressures, Kp, is given by:


Kp =

(PBrCl )2
(2x)2
(2x)2
=
= 7.0
=
(PBr2 )(PCl2 )
(0.30 x)(0.30 x) (0.30 x)2

As Kp is not small, the assumption that 0.30 x ~ x cannot be made. Hence,


(2x)
= 7.0
(0.30 x)
2x = (0.30 x) 7.0 = (0.30 7 ) x 7
x=

(0.30 7 )
(2 + 7 )

= 0.17

The partial pressures at equilibrium are therefore:

PBr2 = PCl2 = 0.30 x = 0.13 atm, PBrCl = 2x = 0.34 atm


p(Br2): 0.13 atm

p(Cl2): 0.13 atm

p(BrCl): 0.34 atm

22/01(a)
Marks
4

CHEM1001

2008-J-8

June 2008

Ammonia, NH3, is produced from nitrogen and hydrogen gas at high temperatures
using the Haber process. At a temperature of 670 K and 50.0 MPa pressure, an
equilibrium mixture was found to contain 0.925 mol nitrogen, 2.775 mol hydrogen
and 1.50 mol ammonia. Write a balanced equation for the Haber process.
N2(g) + 3H2(g)

2NH3(g)

Calculate the mole fraction of each gas in the mixture.


Total number of moles = (0.925 (N2) + 2.775 (H2) + 1.50 (NH3)) mol = 5.20 mol
As mole fraction of A = XA =
=

= 0.178

= 0.534

= 0.288

Calculate the partial pressure of each gas.


The mole fraction, XA, and the partial pressure, pA, are related by:
pA = XA Ptotal
As Ptotal = 50.0 MPa,
= 0.178 50.0 MPa = 8.90 MPa
= 0.534 50.0 MPa = 26.7 MPa
= 0.288 50.0 MPa = 14.4 MPa
Calculate the value for Kp for the reaction at this temperature.
The equilibrium constant in terms of partial pressures is given by:

The partial pressures need to be in atmospheres to be used in this equation.


ANSWER CONTINUES ON THE NEXT PAGE

22/01(a)
Marks
6

CHEM1001

2008-J-8

June 2008

The equilibrium constant in terms of partial pressures is given by:

The partial pressures need to be in atmospheres to be used in this equation.


As 1 atm = 101.3 kPa = 1.013 105 Pa,
= 8.90 MPa =

atm = 88.0 atm

= 26.7 MPa =

atm = 263 atm

= 14.4 MPa =

atm = 142 atm

Hence,

= 1.26 10-5 (dimensionless)


Answer: 1.26 10-5

22/01(a)

CHEM1001

2008-J-9

June 2008

A sample of 0.62 mol CCl4 was placed in a 2.0 L container and heated to a certain
temperature. At equilibrium, [Cl2] = 0.060 M. What is the value of the equilibrium
constant Kc for the following reaction at that temperature?
CCl4(g)

C(s) + 2Cl2(g)

The initial concentration of CCl4 is:


concentration =

.
.

= 0.31 mol L1 = 0.31 M

The reaction table is:


concentration

CCl4(g)

C(s)

2Cl2(g)

start

0.31

change

-x

+2x

equilibrium

0.31-x

2x

As C(s) is a solid, its concentration is essentially constant and is not included in


the equilibrium calculations.
At equilibrium, [Cl2(g)] = 0.060 M and hence x = 0.030 M. Hence at equilibrium,
[CCl4(g)] = (0.31 x) M = 0.28 M.
The equilibrium constant in terms of the concentrations, Kc, is thus:
Kc =

[ ]
[ ]

(.)
(.)

= 0.013
Answer: 0.013

22/01(a)
3

CHEM1001

2009-J-9

June 2009

22/01(a)
Marks
3

Write a balanced equation for the following reaction:


WO3(s) + H2(g) W(s) + H2O(g)
WO3(s) + 3H2(g) W(s) + 3H2O(g)
What is the equilibrium constant expression, Kp, for the above reaction?
The equilibrium constant only involves the gaseous reactants and products. The
equilibrium constant in terms of partial pressures, Kp, is therefore:
Kp =

  
  

What is the equilibrium constant, Kc, for the above reaction, in terms of Kp?
The reaction involves no change in the moles of gas during the reaction: n = 0.
As Kp = Kc(RT)n, for this reaction Kp = Kc.
Fe2O3 can be reduced by carbon monoxide according to the following equation.
Fe2O3(s) + 3CO(g)

2Fe(s) + 3CO2(g)

Kp =19.9 at 1000 K

At 1000 K, what are the equilibrium partial pressures of CO and CO2 if the only gas
initially present is CO at a partial pressure of 0.978 atm?
The reaction table is:

initial / atm
change / atm
equilibrium / atm

Fe2O3(s)

3CO(g)

2Fe(s)

3CO2(g)

0.978
-3x
0.978 3x

0
+3x
3x

The solids do not appear in the equilibrium constant expression and do not need
to be considered. The equilibrium constant in terms of partial pressures, Kp, is
given by:
Kp =

 


 

. 

= 19.9

Hence,
 

. 

= (19.9)1/3 = 2.71

3x = (2.71)(0.978 3x) = 2.65 8.13x or 11.1x = 2.65 or x = 0.238


ANSWER CONTINUES ON THE NEXT PAGE

CHEM1001

2009-J-9

June 2009

From the reaction table,


p(CO) = (0.978 3x) atm = 0.264 atm
p(CO2) = 3x atm = 0.714 atm
p(CO) = 0.264 atm

p(CO2) = 0.714 atm

22/01(a)

CHEM1001

2009-J-10

June 2009

Calculate the standard-free energy change for the oxidation of ammonia to nitric oxide
and water, according to the following equation.
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(l)
Data: fG(NO(g)) = 87.6 kJ mol1
fG(NH3(g)) = 16.5 kJ mol1
fG(H2O(l)) = 237.2 kJ mol1
Using rxnG = mfG(products) - nfG(reactants),
rxnG = ((4 87.6 + 6 -237.2) (4 -16.5)) kJ mol-1 as fG (O2(g)) = 0.
= -1007 kJ mol-1
Answer: -1007 kJ mol-1
Is the reaction spontaneous under standard conditions? Give a reason for your answer.
The reaction is spontaneous as rxnG < 0. This is the condition for a reaction to
be spontaneous.

22/01(a)
Marks
3

CHEM1001

2009-J-11

June 2009

Heating SbCl5 causes it to decompose according to the following equation.


SbCl5(g)

SbCl3(g) + Cl2(g)

A sample of 0.50 mol of SbCl5 is placed in a 1.0 L flask and heated to 450 C. When
the system reaches equilibrium there is 0.10 mol of Cl2 present. Calculate the value of
the equilibrium constant, Kc, at 450 C.
From the chemical equation, 1 mol of Cl2(g) is produced from every 1 mol of
SbCl5(g) that reacts. As 0.10 mol of Cl2(g) is present at equilibrium, 0.10 mol of
SbCl5(g) has reacted. Initially, 0.50 mol of SbCl5(g) was present so the amount
left at equilibrium is (0.50 0.10) mol = 0.40 mol.
From the chemical equation, 1 mol of SbCl3(g) is produced from every 1 mol of
SbCl5(g) that reacts. As 0.10 mol of SbCl5(g) has reacted, 0.10 mol of SbCl3(g) is
present at equilibrium.
[SbCl5(g)]eq =

  




. 

. 

= 0.40 mol L-1 = 0.40 M

. 

= 0.10 mol L-1 = 0.10 M


. 
The equilibrium constant in terms of concentrations, Kc is given by:
[SbCl3(g)]eq = [Cl2(g)]eq =

Kc =


 
 

 

..
.

= 0.025
Answer: Kc = 0.025

22/01(a)
4

CHEM1001

2010-J-8

June 2010

Marks
3

Consider the following equilibrium reaction.


4HCl(g) + O2(g)

2H2O(g) + 2Cl2(g)

Kc = 885 at 500 oC

If 0.030 mol HCl, 0.020 mol O2, 0.090 mol H2O and 0.085 mol Cl2 are mixed in
a 1.0 L container at 500 oC, in what direction will the reaction proceed?
As the gases are present in a 1.0 L container, their concentrations are:
concentration = number of moles / volume
[HCl] = 0.030 mol / 1.0 L = 0.030 M
[O2] = 0.020 mol / 1.0 L = 0.020 M
[H2O] = 0.090 mol / 1.0 L = 0.090 M
[Cl2] = 0.085 mol / 1.0 L = 0.085 M
The reaction quotient, Q, is:
Q=

[ ()] [ ()]
[()] [ ]

(.) [.]
[.] [.]

22/01(a)

= 3600

As Q > Kc, the reaction will proceed towards the reactants.


Answer: towards reactants
What is the value of Kp for the reaction at 500 oC?
The reaction involves 5 mol of gaseous reactants going to 4 mol of gaseous
products. The number of moles of gas decreases in the reaction with n = -1.
Kp and Kc are related by:
Kp = Kc(RT)n
Hence,
Kp = (885) [0.08206 (500 + 273)]-1 = 14
Answer: 14

CHEM1001

2012-J-10

June 2012

Marks
4

Consider the following reaction.


SO2(g) + NO2(g)

SO3(g) + NO(g)

An equilibrium mixture in a 1.00 L vessel was found to contain [SO2(g)] = 0.800 M,


[NO2(g)] = 0.100 M, [SO3(g)] = 0.600 M and [NO(g)] = 0.400 M. If the volume and
temperature are kept constant, what amount of NO(g) needs to be added to the
reaction vessel to give an equilibrium concentration of NO2(g) of 0.300 M?
From the chemical equation,
Keq =

[ ][ ]
[ ][ ]

As the original mixture is at equilibrium:


Keq =

[ ][ ]
[ ][ ]

(.)(.)
(.)(.)

= 3.00

This equilibrium is now disturbed by the addition of x M of NO(g). To reestablish equilibrium, the reaction will shift to the left by an unknown amount y.
The reaction table for this is:

initial

SO2(g)
0.800

NO2(g)
0.100

SO3(g)
0.600

NO(g)
0.400 + x

change

+y

+y

-y

-y

equilibrium

0.800 + y

0.100 + y

0.600 y

0.400 + x - y

As [NO2(g)] = 0.300 M at the new equilibrium, y = (0.300 0.100) M = 0.200 M.


Hence, the new equilibrium concentrations are:
[SO2(g)] = (0.800 + 0.200) M = 1.000 M
[NO2(g)] = 0.300 M
[SO3(g)] = (0.600 0.200) M = 0.400 M
[NO(g)] = (0.400 + x 0.200) M = (0.200 + x) M
As the system is at equilibrium,
Keq =

[ ][ ]
[ ][ ]

22/01(a)

(.)(.!)
(.)(.)

= 3.00

Solving this gives x = 2.05 M. As the reaction is carried out in a 1.00 L container,
this is also the number of moles required.
Answer: 2.05 mol
THE REMAINDER OF THIS PAGE IS FOR ROUGH WORKING ONLY

CHEM1001

2013-J-10

June 2013

Nitrogen and acetylene gases react to form hydrogen cyanide according to the reaction
N2(g) + C2H2(g)

Kc = 2.3 104 at 300 C

2HCN(g)

Write out the equilibrium constant expression for Kc for this reaction as shown
above.

Kc =

[ ]
[ ]

The value of Kp for this reaction at 300 C is also 2.3 104. Why are the values of
Kp and Kc the same for this reaction?
The number of moles of gas remains constant during the reaction. 2 mol of gas
react to give 2 mol of product gas.
Write a balanced equation and calculate the value of the equilibrium constant Kc' for
the formation of 1.0 mol of hydrogen cyanide gas from nitrogen and acetylene gases.
N2(g) + C2H2(g)

HCN(g)

For this reaction, Kc =

[ ]
/ [ ]/

= Kc1/2 = 0.015
Answer: 0.015
What is the equilibrium concentration of HCN(g) if nitrogen and acetylene are mixed
so that both are at starting concentrations of 1.0 mol L1?
The reaction table for this is:

initial

N2(g)
1.0

C2H2(g)
1.0

HCN(g)
0

change

-x

-x

+2x

equilibrium

1.0 - x

1.0 x

2x

Hence, the equilibrium constant expression in terms of x is:


Kc =

[ ]
/ [ ]/

()
(. ! )/ (. ! )/

(. ! )

ANSWER CONTINUES ON THE NEXT PAGE

= 0.015

22/01(a)
Marks
8

CHEM1001

2013-J-10

June 2013

So,
2x = 0.015 0.015x
2.015x = 0.015
x = 0.0074

Hence,
[HCN(g) = 2x N = 0.015 M
(The small x approximation can be used but as no quadratic needs to be solved,
this is unnecessary.)
Answer: 0.015 M

22/01(a)

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