ChE102 Chemistry for Engineers

Final Exam Review package

Waterloo SOS

Fall 2010

Phases Q1
A gaseous compound known to contain only carbon, hydrogen, and nitrogen is mixed with exactly the
volume of oxygen required for its complete combustion to CO2, H2O, and N2. Burning 20 litres of the
gaseous reaction mixture (the unknown compound plus oxygen) produces 14 litres of CO2, 10 litres of
H2O vapour, and 2 litres of N2, all at the same temperature and pressure.
(a) Of the 20 litres of reaction mixture, how many litres are oxygen?
(b) What is the molecular formula of the unknown compound?

Basis: 20 litres of the reaction mixture containing (20-a) litres of CxHyNz plus a volumes of O2.
For an ideal gas at constant temperature and pressure, the volume of the ideal gas is directly proportional
to the number of moles of the ideal gas. Therefore, the volume ratios given in the problem statement can
also be interpreted as molar ratios.
The chemical equation for the reaction is therefore:

(20 a ) C x H y N z + a O 2 14 CO 2 + 10 H 2 O + 2 N 2
Balancing this chemical equation for C, H, N, and O gives four equations:

Carbon(C ) : (20 a ) x = 14

Hydrogen( H ) : (20 a ) y = 20
Nitrogen( N ) : (20 a ) z = 4
Oxygen(O) : 2 a = 38
The solution to these equations is:

a = 19
x = 14 ,

y = 20 ,

z=4

Of the 20 litres of reaction mixture, 19 litres are O2, and the molecular formula of the unknown compound
is C14H20N4.
Phases Q2
Dew point is defined as the temperature at which the vapour pressure of water is equal to the partial
pressure of water vapour in an air sample. Exactly 0.105 g of water was evaporated into 10.0 L of dry air
at 60.0C and 100 kPa. Using the vapour pressure data below, estimate the dew point of the moist air
sample if the total pressure is maintained at 100 kPa.
Data:
T [K]
P [kPa]
o

280
0.9912

285
1.388

290
1.919

295
2.620

Basis: 0.105 g of H2O in 10.0 L of dry air at 60.0 oC and 100 kPa.
Data: Molecular mass of H2O, H 2O = 18.01528 g mol

298.15
3.197

The number of moles of H2O evaporated is,

0.105 g H2O
n
=
H 2O

The number of moles of dry air is,

P V
100 kPa
ndry air =

R T

mol H2O
18.01528 g H2O

10.0 L
333.15 K

= 0.0058284 mol H2O

mol K
8.31451 kPa L

= 0.36101 mol dry air

The partial pressure of H2O in the humid air is therefore,

0.0058284 mol
100 kPa = 1.5888 kPa
PH 2O = y H 2O Ptotal =
0.0058284 mol + 0.36101 mol

The dew point temperature of the humid air is the temperature at which this partial pressure of H2O
becomes equal to the vapour pressure of H2O. Inspection of the given vapour pressure data shows that
the dew point temperature should fall between 285 K and 290 K. Since the Clausius-Clapeyron equation
states that,
Po
ln 1o
P
2

H vap
=

1
1

T
T
2
1

we find that between 285 K and 290K,

H vap 1
1.388 kPa
1
=

ln

R 285 K 290 K
1.919 kPa
H vap

= 5354.734 K
R

Therefore,

1.5888 kPa
1
1
= (5354.734 K )
ln

Tdew point 285 K

1.388 kPa

Tdew point = 287.06 K

The dew point temperature of the humid air is 287.06 K or 13.91oC.

Phases Q3
At 25.0C, the vapour pressure of trichloroethene (C2HCl3) is 73.00 mm-Hg. At the same temperature,
the vapour pressure of chloroform (trichloromethane, CHCl3) is 199.1 mm-Hg.
a) What is the pressure exerted by a solution containing 32.05% by mass of C2HCl3 (the balance
being CHCl3) at 25.0C?
b) What is the vapour phase mole fraction of CHCl3 that is in equilibrium with the liquid solution
specified in (a)?

Basis: 100 g of solution containing 32.05 g of C2HCl3 and 67.95 g of CHCl3 at 25.0C.
Data: Molecular masses in g/mol:
C2 HCl3 = 131.388
CHCl3 = 119.377

The composition of the C2HCl3-CHCl3 solution is given in the following table:

Component Mass [g] Mole [mol] Mole fraction
32.05
0.243934
0.29999
C2HCl3
67.95
0.569205
0.70001
CHCl3
0.813139
1.00000
Total
The total vapour pressure is
o
Ptotal = xC2 HCl3 PCo2HCl3 + xCHCl3 PCHCl
3

= 0.30 73.00 mm Hg + 0.70 199.1 mm Hg

= 161.2712 mm Hg
The total vapour pressure exerted by the solution is 161.271 mm-Hg.

Basis: 100 g of solution containing 32.05 g of C2HCl3 and 67.95 g of CHCl3 at 25.0C.
The vapour phase mole fraction of CHCl3 is
y CHCl 3 =

PCHCl 3
Ptotal

o
x CHCl 3 PCHCl
3

Ptotal

0.70
=

199.1 mm-Hg
161.271 mm-Hg

= 0.864208

The mole fraction of CHCl3 in the vapour phase is 0.8642.

Phases Q4
The vapour pressure of pure liquid CS2 is 0.3914 atm at 20C. When 40.0 g of rhombic sulphur is
dissolved in 1.00 kg of CS2, the vapour pressure of CS2 falls to 0.3868 atm. Determine the molecular
formula for the sulphur molecules dissolved in CS2.
Basis: 1.0 kg of CS2 liquid.
Data: Initial vapour pressure of CS2, 0.3914 atm.
Mass of sulphur added, 40.0 g.
Final vapour pressure of CS2, 0.3868 atm.
Molecular mass of CS2, CS2 = 76.143 g mol
Atomic mass of sulphur, S = 32.066 g mol
We know what the change in pressure is due to the addition of sulphur to the CS2 solution. Thus the mole
fraction of rhombic sulphur present is
P
(0.3868 0.3914) atm
x rS = o =
= 0.011753
PCS2
0.3914 atm
The solution contains 1.0 kg of CS2, which is
1000 g CS2
n
=
CS2

mol CS2
76.143 g CS2

= 13.13318 mol CS2

From the expression for mole fraction we can find the number of moles of rhombic sulphur added,
x rS =

n rS
n rS + n CS2

n rS =

x rS n CS2
1 x rS

= 0.15619 mol rS

Since we know the mass of rhombic sulphur added, we can find the molecular weight of rhombic sulphur,
40.0 g rS
rS =
= 256.10533 g/mol rS
0.15619 mol rS
To find the number of sulphur atoms in rhombic sulphur,
256.10533 g/mol
rS
=
S
32.066 g/mol

= 7.9868

Therefore rhombic sulphur is of the form S8.

Phases Q5
The vapour pressure of benzene is 1.34 atm at 90oC and its boiling point at 1 atm is 80oC. Assuming that
Hvap is constant, calculate the pressure at which benzene will boil at 0oC.
From the Clapeyron equation:

ln
ln

P2

P1

H vap 1 1

R T1 T2

H vap
1atm
=
1.34atm
R

o
H vap
P3
ln
=
1.34atm
R

1
1

(90 + 273.15) K (80 + 273.15) K

1
1

(
)
(
)
90
+
273
.
15
K
0
+
273
.
15
K

P3 = 0.04446atm
The pressure is 0.044476atm 760 mmHg atm-1 = 33.8 mmHg
Phases Q6
Diethyl ether (C4H10O) is a volatile, highly flammable organic liquid that is used mainly as a solvent. The
vapour pressure, Pvap, of diethyl ether can be estimated using Antoines equation,

ln Pvap (mmHg ) = A

B
T (K ) + C

where A = 16.0828, B = 2511.29 K, C = -41.95 K for diethyl ether. Calculate the enthalpy of vaporization
of diethyl ether at 25oC and 45oC and use these values to estimate the heat of vaporization for diethyl
ether.

ln Pvap ,1 = 16.0828

2511.29
= 531.12 mmHg
(25 + 273) 41.95

ln Pvap , 2 = 16.0828

2511.29
= 1080.93 mmHg
(45 + 273) 41.95

Use Clausius-Clapeyron equation to estimate Hvap:

Pvap , 2 H vap 1 1

ln
=
R T1 T2
Pvap ,1
1

H vap

1
Pvap , 2 1 1
1
J
kJ
1080.93 1

= R ln

= 8.31451
ln

= 27994.23
P T T
mol.K 531.12 298 K 318 K
mol
2
vap ,1 1

Phases Q7
A salt AB2 dissociates partially in water. The dissociate occurs as,
AB2 A 2+ + 2 B

A 0.10 molal aqueous solution of AB2 has a freezing point of 0.250C. Calculate the degree of
dissociation of the salt, assuming that it is independent of temperature.
Data:

K f = 1.86 kg o C mol for H 2 O

Basis: 0.10 molal aqueous solution of AB2 containing 1 kg of H2O.

From the freezing point depression we can calculate the effective molality of the solution.
T f
0.250oC
mol
mol
m eff =
=
= 0.13441
o
Kf
1.86 kg C
kg H2O
Let be the degree of dissociation of AB2 in the solution (i.e., is equal to the fraction of AB2 that
dissociates in solution). Thus, we have in the solution,
n AB2 = 0.10 (1 ) mol AB 2 (undissociated)
n A2 + = 0.10 mol A 2+
n B- = 0.20 mol B-

The effective molality is,

n AB2 + nA 2+ + n B1 kg H 2 O

Solving this equation

[0.10 (1 ) + 0.10 + 0.20 ] mol = [0.10 + 0.20 ] mol = 0.13441 mol

1 kg H 2 O

1 kg H 2 O

1 kg H 2 O

 0.13441 mol

1 kg H 2 O 0.10 mol
1 kg H 2 O

=
0.20 mol

The degree of dissociation of AB2 in water is 0.17205.

Phases Q8
A saturated solution is prepared at 70C containing 32.0g CuSO4 per 100.0 g solution. A 335 g sample of
this solution is then cooled to 0C and CuSO45H2O precipitates. If the concentration of a saturated
solution at 0C is 12.5 g CuSO4/100 g solution, what mass of CuSO45H2O precipitate would be obtained?
(Hint: Note that the solution composition is stated in terms of CuSO4 and that the solid that precipitates is
the copper sulphate hydrate, CuSO45H2O).
Basis: 335 g of solution containing 32.0 g of CuSO4 per 100 g
Data:

Molecular masses in g mol-1:

CuSO = 159.607
4

CuSO

5H 2 O

= 249.681

CuSO4 dissolved initially:

min, CuSO = 335 g soln
4

CuSO4 dissolved at end:

mf,CuSO 4 = (335 x) g
soln

32.0 g CuSO4
100 g soln

12.5 g CuSO4

107.2 g CuSO4

0.125 * (335 m)
g CuSO4

100 g soln
Where m is the mass (g) of CuSO45H2O precipitate.
The mass fraction of CuSO4 in the CuSO45H2O precipitate is
159.607 g CuSO4
1 mol CuSO4
1 mol precipitate
x=
mol CuSO4
1 mol precipitate 248.681 g precipitate

0.639 244 g
CuSO4/g precipitate

Mass balance on CuSO4:

Mass dissolved at
start
107.2

mass dissolved at end

mass precipitated

0.125 * ( 335 m)

0.639 244 * m

Solving, mass of precipitate, m = 127 g.

Phases Q9
The vapour pressure of pure water water is 17.54 mm-Hg at 20oC. Calculate the vapour pressure
lowering of aqueous solutions that are 0.25 molality in
a) NaCl,
b) CaCl2,
c) sucrose (C12H22O11).
Basis: 0.25 mol of NaCl in 1000 g of H2O.
Data: Molecular mass of H2O, H 2O = 18.01528 g mol
The number of moles of H2O is
1000 g H2O

1 mol H2O
18.01528 g H2O

= 55.50844 mol H2O

Assuming complete dissociation of NaCl in the solution, the numbers of moles of Na+ and Cl- in the
solution are both 0.25 mol. The vapour pressure lowering of the solution is,

n Na + + n Cl
PH 2O =
n + + n + nH O
Cl
2
Na

o
PH O
2

0.25 mol + 0.25 mol

17.55 mm - Hg
=
0.25 mol + 0.25 mol + 55.50844 mol
= 0.15658 mm - Hg

The vapour pressure lowering of the aqueous solution is 0.1566 mm-Hg.

Basis: 0.25 mol of CaCl2 in 1000 g of H2O.

Data: Molecular mass of H2O, H 2O = 18.01528 g mol
Assuming complete dissociation of CaCl2 in the solution, the numbers of moles of Ca2+ and Cl- in the
solution are 0.25 mol and 0.50 mol respectively. The vapour pressure lowering of the solution is,

nCa 2 + + n Cl
PH 2O =
n 2+ + n + nH O
Cl
2
Ca

o
PH O
2

0.25 mol + 0.50 mol

17.55 mm - Hg
=
0
.
25
mol
+
0
.
50
mol
+
55
.
50844
mol

= 0.23383 mm - Hg

The vapour pressure lowering of the aqueous solution is 0.2338 mm-Hg.

Basis: 0.25 mol of C12H22O11 in 1000 g of H2O.

Data: Molecular mass of H2O, H 2O = 18.01528 g mol

Assuming no dissociation of C12H22O11 in the solution, the number of moles of C12H22O11 in the solution
is 0.25 mol. The vapour pressure lowering of the solution is,

nC12 H 22O11
PH 2O =
nC H O + n H O
2
12 22 11

o
PH O
2

0.25 mol
17.55 mm - Hg
=
0.25 mol + 55.50844 mol
= 0.078643 mm - Hg

The vapour pressure lowering of the aqueous solution is 0.07864 mmHg.

Phases Q10
An aqueous solution is 15.0% by weight with respect to NaBr. Assuming that the solution behaves
ideally and that dissociation is complete, what would be the expected boiling point of the solution at a
total pressure of 1 atm?
Data:

K b = 0.512 kg C mol for H 2 O

Basis: 100.0 g of NaBr solution containing 15.0g of NaBr.

Data: Molecular mass of NaBr, NaBr = 102.8938 g mol
Sodium bromide dissociates in aqueous solution as,
+

NaBr(s) Na (aq)
+ Br(aq)

The effective molality of the solution is,

15 g NaBr
mol NaBr
m eff =
85 g H2O 102.8938 g NaBr

2 mol Na+ and Br- ions

1 mol NaBr

The boiling point elevation of the solution is

3.4302 mol
Tb = meff K b =
kg

1000 g H2O
1 kg H2O

0.512 kg oC
mol

= 3.4302

mol ions
kg H2O

= 1.756oC

The boiling point of the NaBr solution is 101.76oC at 1 atm.

Phases Q11
At 90.0oC, the vapour pressures of benzene (C6H6) and toluene (C7H8) are 1.34 atm and 0.534 atm,
respectively. Benzene and toluene form a nearly ideal solution at 90.0oC.
a) What is the mole fraction of toluene in a benzene-toluene solution that begins to boil at 90.0oC
under 1 atm?
b) What is the mass percentage of benzene in the vapour over this solution at 90.0oC and 1 atm?
Basis: 1 mol of benzene-toluene solution boiling at 1 atm and 90.0oC.

Let x C7 H 8 represent the mole fraction of toluene in the liquid solution. The total vapour pressure over the
solution, using Raoult's law, is

Ptotal = PC6 H 6 + PC7 H 8 = 1 x C7 H 8 PCo6 H 6 + x C7 H 8 PCo7 H 8 = 1 atm

Since PCo6 H 6 = 1.34 atm and PCo7 H 8 = 0.534 atm at 90.0oC, solving for x C7 H 8 gives a toluene mole fraction of
0.4218 in the liquid solution.
Basis: 1 mol of benzene-toluene vapour in equilibrium with the boiling solution at 1 atm and 90.0oC.
Data: Molecular masses in g/mol:
C6 H 6 = 78.1134
C7 H 8 = 92.1402

The mole fractions of benzene and toluene in the vapour phase are,
0.57816 1.34 atm
PC H
x C H PCo H
y C6 H 6 =

y C7 H 8 =

Ptotal
PC7 H 8
Ptotal

Ptotal
x C7 H 8 PCo7 H 8
Ptotal

1 atm
0.42184

= 0.77474

0.534 atm

1 atm

The mass fraction of benzene in the vapour phase is therefore

60.5175
y C6 H 6 C6 H 6
wC6 H 6 =
=
y C6 H 6 C6 H 6 + y C7 H 8 C7 H 8
81.2731

= 0.22526

= 0.74462

The mass percentage of benzene in the vapour phase is 74.46 %.

Phases Q12
The boiling point of hexane, C6H14, is 68.7oC at 1 atm. The vapour pressure of heptane, C7H16, is 200
mm-Hg at 58.7oC and 400 mm-Hg at 78.0oC. Assuming that hexane and heptane form an ideal liquid
solution, calculate the mole fractions of hexane in the liquid and vapour phases in equilibrium with each
other at 68.7oC and a total pressure of 70 kPa.
Basis: System of hexane and heptane in vapour-liquid equilibrium at 68.7oC and 70 kPa.
First of all we need to estimate the vapour pressure of heptane at 68.7oC. Using the given vapour pressure
data and the Clausius-Clayperon equation, we get
H vap
R

Po
= ln 1o
P
2

T
1 T2

200 mm - Hg

1
1

= ln

400 mm - Hg 331.85 K 351.15 K

Thus, at 68.7oC, the vapour pressure of heptane is approximately

= 4185.07 K

PCo7 H16 (341.85 K ) = P1o e

H vap
1
1

R T341.85 K T1

1
1

(4185.07 K )

341.85 K 331.85 K

= (200 mm - Hg )
= 289.23 mm - Hg

= 38.561 kPa at 68.7 o C

The liquid phase mole fractions can be determined using Raoult's law.

Ptotal = PC6 H14 + PC7 H16 = x C6 H14 PCo6 H14 + 1 x C6 H14 PCo7 H16 = 70 kPa

Since PCo6 H14 = 101.325 kPa and PCo7 H16 = 38.561 kPa, solving the above equation gives x C6 H14 = 0.50091. The
mole fraction of hexane in the vapour phase is then
y C6 H14 =

PC6 H14
Ptotal

x C6 H14 PCo6 H14

Ptotal

0.50091

101.325 kPa

70 kPa

= 0.72506

The mole fractions of hexane in the liquid and vapour phases are 0.5009 and 0.7251, respectively.
Phases Q13
A 4.0 g mixture consisting of sucrose (C12H22O11) and zinc nitrate (Zn(NO3)2) is dissolved in 150.0 g of
water. If the resulting solution freezes at 0.768C, what is the mass fraction of sucrose in the mixture?
Assume that Zn(NO3)2 dissociates completely in water.
K f = 1.86 kg o C mol for H 2 O

Data:

Basis: 4.0 g of the C12H22O11-Zn(NO3)2 mixture containing x g of C12H22O11 dissolved in 150.0 g of

H2O.
Data: Molecular masses in g/mol:
C12 H 22O11 = 342.30
Zn (NO3 )2 = 189.40

Zinc nitrate dissociates in aqueous solution as

Zn(NO 3 )2 Zn 2 + + 2 NO 3

The effective molality of the solution is (eqn. 1),

meff =

x g C12 H 22 O11
mol C12 H 22 O11
1

0.150 kg H 2 O
342.30 g C12 H 22 O11
+

(4.0 x ) g Zn(NO 3 )2

mol Zn (NO 3 )2
3 mol ions

= (0.42239 0.08612 x ) mol kg

189.40 g Zn (NO 3 )2 1 mol Zn (NO 3 )2

But the effective molality can also be calculated from the freezing point depression as (eqn. 2)
T f
0.768 oC
mol
= 0.412903226 mol/kg
m

1.86 kg oC
Therefore equating eqn. 1 and 2.
(0.42239 0.08612x) mol/kg = 0.412903226 mol/kg
Solving for x gives x = 0.110116114 g.
The mass fraction of sucrose in the mixture is therefore x g/4.0 g = 0.0275.
Phases Q14
A solution of 0.07265 g of a human hormone in 100 mL of solution has an osmotic pressure of 12.60
mmHg at 21.6 oC. What is the molecular mass of the hormone in g /mol?

Basis: 0.07265 g of hormone in 100 mL.

The osmotic pressure is given by:
=

n R T m R T
=
V
V

Solving for the molecular mass

=

m R T
=
V

0.07265 g
-2

1.65810 atm

0.082 Latm
molL

294.6 K
0.1 L

= 1058.5 g/mol

The molecular mass of the hormone is 1058 g/mol.

Phases Q15
At 100oC the vapour pressure of toluene is 557.2 mmHg. Toluene and benzene form nearly ideal
solutions. A particular benzene-toluene solution has a normal boiling point of 100oC, and the vapour in
equilibrium with the liquid contains 58.26% toluene by mass. What is the composition of the liquid,
expressed as a mass percentage of toluene? Solve this without looking up the vapour pressure of benzene.
Basis: 100 g of benzene-toluene vapour in equilibrium with its liquid solution at 100oC.
Data: Molecular masses in g/mol:
C6 H 6 = 78.1134
C7 H 8 = 92.1402

The following table shows the composition of the vapour phase:

Component mass [g]
mol
toluene
58.26
0.6323
benzene
41.74
0.5344
Total
100.00
1.1666

y
0.5420
0.4580
1.0000

The mole fraction composition of the liquid phase is

0.5420
PC7 H 8
y C7 H 8 Ptotal

760 mmHg

PCo7 H 8

557.2 mmHg

x C7 H 8 =

PCo7 H 8

= 0.7392

The mass percentage of toluene in the liquid phase is therefore

x C7 H 8 C7 H 8
wC 7 H 8 =
(1 xC7H8 ) C6H6 + xC7H8 C7H8 = 0.7697
The liquid phase contains 76.97% toluene by mass.

Equilibrium Q1
Consider the homogeneous gas phase reaction
A ( g ) + B( g ) R ( g )

occurring at 400.0 K in a 1.0 L vessel. Initially there are 0.070 mol of A, 0.030 mol of B and 0.150 mol
of R. What is the equilibrium concentration of R (in mol/L)?
Data:

for the above reaction at 400.0 K: K P = 0.9749 atm 1

Basis: 0.070 mol of A, 0.030 mol of B, and 0.150 mol of R in a 1.0 L vessel at 400.0 K.
The net change in the number of moles in the reaction (n) is 1. Therefore, conversion of KP into Kc
gives
0.9749 0.0820578 atm L 400.0 K
= 31.9993 L/mol
K c = K P (R T ) n =
atm
mol K
The stoichiometry of the reaction is summarised in the following table:
Component initial [mol] change [mol] final [mol]
A
0.070
x
0.070x
B
0.030
x
0.030x
R
0.150
+x
0.150+x

concn. final [mol/L]

0.070x
0.030x
0.150+x

When equilibrium is reached,

Q=

[R ] =
[A][B]

0.150+x
(0.070-x)(0.030-x)

= Kc = 31.9993 L/mol

Rearranging this gives the quadratic equation:

31.9993 ( x ) 4.19993 ( x ) 0.08280147 = 0

2

Solving for x:

0.14865719128
x=
- 0.01740650767

extraneous root : causes (0.070 - x ) < 0

The concentration of R at equilibrium is (0.150+x) mol/L = 0.1326 mol/L.

Equilibrium Q2
Consider the homogeneous gas phase reaction:
A (g ) + B (g ) R (g ) + S (g )

at equilibrium, the partial pressures are PA=0.30 atm, PB=0.70 atm, PR=0.25 atm, and PS=0.15 atm at
300.0 K.
a) Calculate the equilibrium constants Kc and KP at 300.0 K.
b) Is this a fast or a slow reaction?
c) How is equilibrium affected if the total pressure of the system is doubled at constant temperature?
d) How is equilibrium affected if the absolute temperature of the system is doubled at constant
pressure?
Basis: Equilibrium partial pressures of PA=0.30 atm, PB=0.70 atm, PR=0.25 atm, and PS=0.15 atm at
300.0 K.
Calculation of the equilibrium constants gives:
0.25 atm 0.15 atm
P P
KP = R S =
= 0.178571429
PA PB
0.30 atm 0.70 atm

K c = K P (R T )

= 0.178571429 since n=0

The equilibrium constants at 300.0 K are KP=Kc=0.1786.

No information is provided regarding the actual rate of reaction.

Since n=0 for this reaction, KP is not dependent on Ptotal, and doubling the total pressure of the system at
constant temperature has no effect on equilibrium.

Increasing the temperature would cause the reaction to proceed in an endothermic direction, which is not
specified in this problem.

Equilibrium Q3
.For the homogeneous gas phase reaction
2 A ( g ) R (g )

at 600.0 K, Kc = 45.0 L/mol. At equilibrium at 600.0 K, the total pressure of the system is 27.08 atm and
the mole fraction of R is yR = 0.818181. This mixture is compressed at 600.0 K to one-half the initial
volume, and the system is allowed to proceed to a new equilibrium state.
a) What is the concentration of R (in mol/L) at the new equilibrium state?

b) What is the total pressure at the new equilibrium state?

Basis: Initial total volume of gases of V L at 600.0 K and 27.08 atm.

The initial moles of A and R are
nA =

PA V y A Ptotal V
=
=
R T
R T

0.181818

27.08 atm
600 K

molK
0.0820578 atmL

= 0.1000V mol A

nR =

PR V y R Ptotal V
=
=
R T
R T

0.818181

27.08 atm
600 K

molK
0.0820578 atmL

= 0.4500V mol R

The stoichiometry of the reaction is summarised in the following table.

Component initial [mol] change [mol] final [mol]
(0.10A
0.10V
2xV
2x)V
R
0.45V
+xV
(0.45-x)V
At the final equilibrium state,
Kc =

[R ]
[A]2

0.45 + x
2 (0.10 2 x )2

concn. final [mol/L]

(0.10-2x)V/0.5V
(0.45-x)V/0.5V

= 45.0 L/mol

Rearranging this gives the quadratic equation

360 x 2 37 x + 0.45 = 0

Solving,

0.088683 extraneous root : causes(0.10 - 2 ) < 0

x=
0.014095

The concentration of R at the new equilibrium state is [(0.45+x)/0.5] mol/L = 0.9282 mol/L.

Equilibrium Q4
At 1000 K, the two reactions
C (s ) + CO 2 (g ) 2 CO (g )

(1)

CO (g ) + H 2 O (g ) CO 2 (g ) + H 2 (g )

(2)

have equilibrium constants KP(1) = 1.900 atm for reaction (1) and KP(2) = 1.374 for reaction (2).
a) Calculate the equilibrium constant at 1000 K for the overall (water-gas) reaction.
C (s ) + H 2 O (g ) CO (g ) + H 2 (g )

b) Initially the system contains only C and water vapour at 2.0 atm and 1000 K. Calculate the
partial pressure of CO at equilibrium.

Basis: Reactions (1) and (2) as stated in the problem.

Since the water-gas reaction is obtained by simply be the addition of reactions (1) and (2), the equilibrium
constant of the water-gas reaction at 1000 K is KP = KP(1) KP(2) = 1.900 atm 1.374 = 2.6106 atm.

Basis: Initial conditions PH 2O = 2.0 atm and 1000 K.

Assumption: The reaction occurs in a constant volume vessel at constant temperature; C(s) is supplied in
an excess amount.
Since the reaction is isothermal and occurs in a constant volume vessel, Pi ni by Dalton's law. The
stoichiometry of the reaction is summarised in the following table.
Component
initial [atm]
change [atm]
final [atm]
H2O
2.0
2.0P
P
CO
0.0
+P
P
H2
0.0
+P
P
At the final equilibrium state,
QP =

PCO PH 2
PH 2O

= KP

(P )2
2.0 P

= 2.6106 atm

which leads to the quadratic equation,

(P )2 + 2.6106 (P ) 5.2212 = 0
Solving for P gives,
1.32624
P =
3.93684 extraneous root : causes negative Pi

The partial pressure of CO at equilibrium is PCO=P=1.326 atm.

Equilibrium Q5
Consider the successive homogeneous gas phase reactions
3 A (g ) 2 B (g )

(1)
B ( g ) + C ( g ) D (g )
(2)
-1
The equilibrium constants for these two reactions at 500.0 K are KP(1) = 6.0932 atm for reaction (1) and
Kc(2) = 10.0 L/mol for reaction (2).
a) What is the value of Kc for the overall reaction at 500.0 K?
b) What is the value of KP for the overall reaction at 500.0 K?
Basis: Reactions (1) and (2) as stated in the problem statement.
For reaction (1), since the change in the number of moles (n) is 1,
6.0932 0.0820578 atmL 500 K
K c (1) = K P (1) (R T ) =
atm
molK

= 249.997 mol/L

The overall reaction is 3 A (g ) + 2 C (g ) 2 D (g ) is obtained by adding twice reaction (2) to reaction (1).
Thus,
K c (overall ) = K c (1) K c2(2 ) = 249.997 L/mol (10.0 L/mol)2 = 24999.7 L3 /mol 3

The overall equilibrium constant based on concentration is Kc = 24999.7 L3/mol3.

Basis: The overall reaction 3 A (g ) + 2 C (g ) 2 D (g ) .
For the overall reaction,
K P (overall ) =

K c (overall )

(R T )

24999.7 L3
mol3

(molK)3
(0.0820578 atmL)3

(500 K)3

= 0.361964 atm-3

The overall equilibrium constant based on partial pressures is KP = 0.36196 atm-3.

Equilibrium Q6
Lead fluoride (PbF2) is slightly soluble in water. The dissociation reaction is
PbF2 (s ) Pb 2 + (aq ) + 2 F - (aq )

for which Ksp = 3.710-8 mol3/L3 at 300 K.

a) Calculate the solubility of PbF2 at 300 K.
b) If an excess of PbF2 were added to a solution of 10-3 M NaF, what would be the equilibrium
concentration of Pb2+?

Basis: 1.0 L of saturated aqueous PbF2 solution containing n mol of dissolved and dissociated PbF2.
In 1.0 L of saturated PbF2 solution containing n mol of dissociated PbF2, there are n mol of Pb2+ and 2n
mol of F-. Therefore,

][ ]

Q = Pb 2+ F

= K sp (PbF )
2

(n )(2n )2 = 3.7 10 8 mol 3 /L3

4n 3 = 3.7 10 8 mol 3 /L3
n = 2.0992 10 3 mol/L

The solubility of PbF2 in water is 2.09910-3 mol/L.

Basis: 1.0 L of 10-3 M aqueous NaF solution.
Assumption: NaF is completely dissociated in the 10-3 M aqueous solution and the addition of PbF2 is not
sufficient to cause NaF to precipitate.
Ia at equilibrium n mol of PbF2 dissolves and dissociates into the 10-3 M NaF solution, then the number of
moles of Pb2+ and F- in the solution are n mol and (0.001+2n) mol, respectively. Therefore

][ ]

Q = Pb 2 + F

= K sp (PbF )
2

(n )(0.001 + 2n )2 = 3.7 10 8 mol 3 /L3

4n 3 + 0.004n 2 + 0.000001n 3.7 10 8 = 0

This is a cubic equation in n. Solving for n by trial-and-error or by Newton-Raphson iteration gives n =

1.779810-3. Thus the concentration of Pb2+ at equilibrium is 1.78010-3 mol/L.
Equilibrium Q7
Suppose that the PbF2 in the previous problem was impure and contained some PbSO4. If excess amounts
of both compounds were added to pure water, what would be the concentrations of all the dissolved
species at equilibrium? Lead sulphate dissociates as
PbSO 4 (s ) Pb 2+ (aq ) + SO 24- (aq )

and K sp (PbSO ) = 1.3 10 8 mol 2 /L2 at 300 K.

4

Basis: 1.0 L of aqueous solution saturated in both PbF2 and PbSO4.

Let n F and nSO 2- be the numbers of moles of F- and SO42- in the 1.0 L of saturated solution. The number
4

of moles of Pb2+ in the saturated solution is therefore n Pb 2+ = 0.5 n F + nSO2 mol . Equilibrium of the
dissociation of PbF2 and PbSO4 requires that

][ ] = (0.5 n

Q PbF2 = Pb 2+ F

][

] (

)( )

+ nSO 2 n F
4

= K sp (PbF ) = 3.7 10 8 mol 3 /L3

)( )

QPbSO 4 = Pb 2+ SO 24 = 0.5 nF + nSO 2 nSO 2 = K sp (PbSO ) = 1.3 10 8 mol 2 /L2

4

(1)

(2)

Dividing equation (1) by equation (2) gives

(n F )2 = 13..37 (nSO

2
4

Substituting equation (3) into equation (1) or (2) and solving the system of equations eventually gives
n Pb 2+ = 2.10329 10 3 mol/L
n F = 4.19422 10 3 mol/L
nSO2- = 6.18079 10 3 mol/L
4

The concentration of the ions in solution are [Pb2+]=2.10310-3 mol/L, [F-]=4.19410-3 mol/L, and [SO42]=6.18110-6 mol/L.
Equilibrium Q8
For the reaction
SO 2 Cl 2 ( g ) SO 2 ( g ) + Cl 2 ( g )

the equilibrium constant KP is 2.4 atm at 375 K and 0.0144 atm at 300 K.
a) Is the reaction endothermic or exothermic?

b) Express the degree of dissociation of SO2Cl2 at equilibrium as a function of the total pressure and
KP. Start with pure SO2Cl2.
Basis: KP= 2.4 atm at 375 K and KP = 0.0144 atm at 300 K.
The equilibrium constant KP increases as temperature increases. The reaction is endothermic.
Basis: 1.0 mol of pure SO2Cl2.
The following table gives the reaction stoichiometry
SO2Cl2
Initial
1
Change
x
Final
1x

SO2

+x
x

Cl2

+x
x

At equilibrium, the partial pressures of the gases are

1 x
Ptotal
1+ x
x
=
Ptotal
1+ x

PSO2Cl2 =
PSO2 = PCl2

The equilibrium constant is therefore

KP =
=

PSO2 PCl2
PSO 2Cl 2
x2
1 x2

x2
P
(1 x ) (1 + x ) total

Ptotal

The degree of dissociation of SO2Cl2 is

= 1
=

moles of SO 2 Cl 2 at equilibrium
1 x
= 1
=x
initial moles of SO 2 Cl 2
1

KP
Ptotal + K P

The degree of dissociation of SO2Cl2 is (KP/Ptotal+KP).

Electrochemistry Q1
Balance the following reactions (not all are RedOx reactions)
a)

2+

UO 2 (aq ) + Te (s ) acid

U (4aq+ ) + TeO 24(aq )

b) SiCl 4 ( aq )
SiO 2 (s ) + Cl (aq )
base

c)

As 2 O 3 (s ) + NO 3 (aq ) acid

H 3 AsO 4(aq ) + NO ( g )

The two-half reactions are

2+

reduction
UO 2 (aq ) + 4 H 3O (+aq ) + 2 e

U (4aq+ ) + 6 H 2 O (l )

Te (s ) + 12 H 2 O (l ) oxidation

TeO 24(aq ) + 8 H 3 O (+aq ) + 6 e

The complete reaction is
2+

acid
3 UO 2 (aq ) + Te (s ) + 4 H 3O (+aq )
3 U (4aq+ ) + TeO 24(aq ) + 6 H 2 O (l )

The complete reaction (not a RedOx reaction) is

SiCl 4 (aq ) + 4 OH (aq ) base

SiO 2 ( s ) + 4 Cl (aq ) + 2 H 2 O (l )

The two-half reactions are

NO 3 (aq ) + 4 H 3 O (+aq ) + 3 e reduction

NO (aq ) + 6 H 2 O (l )
As 2 O 3 (aq ) + 9 H 2 O (l ) oxidation

2 H 3 AsO 4 (aq ) + 4 H 3O (+aq ) + 4 e

The complete reaction is
acid
3 As 2 O 3 (aq ) + 4 NO 3 (aq ) + 3 H 2 O (l ) + 4 H 3O (+aq )
6 H 3 AsO 4 (aq ) + 4 NO (aq )

Electrochemistry Q2
a) What is the mass of Cl2 gas that can be produced by the electrolysis of molten NaCl with a
current of 100 A for 1 hour?
b) In the electrolysis of Na2SO4, the anode reaction is
6 H 2 O (l ) 4 H 3O (+aq ) + O 2 ( g ) + 4 e
o = 1.229 V
A cell operates with steady current for 90 minutes. The amount of O2 (g) produced is measured to
be 0.98 L at 25.0oC and 100.0 kPa. What is the current through the electrolysis cell?

Basis: One hour of electrolysis operation.

The half-reaction for the oxidation of chlorine is
2 Cl Cl 2 ( g ) + 2 e

Thus
1 hour 3600 s 100 A
1 hour

1C
1
As

1 mol e96485.31 C

The mass of Cl2 that can be produced is 132.98 g.

Basis: 0.98 L of O2 (g) at 25.0oC and 100.0 kPa.

1 mol Cl2 70.9054 g Cl2

2 mol e-

1 mole Cl2

= 132.279 g Cl2

Thus
0.98 L O2

molK

90 minutes

8.31451
kPaL

100 kPa

4 mol e-

96485.31 C 1 minute
1 mol e-

298.15 K 1 mol O2

60 s

1
As

= 2.825 A

1C

The current is 2.825 A.

Electrochemistry Q3
Consider the two half-reactions
+

3+
o
Ce (4aq
) + e Ce (aq ) , = 1.700 V

Cl 2 (g ) + 2 e 2 Cl (aq ) , o = 1.358 V

a) Combine and balance the two half-reactions to give the spontaneous reaction under standard
conditions in acid media.
b) Calculate the cell potential at 25.0oC for [Ce4+] = 0.02 M, [Ce3+] = 2.0 M, [Cl-] = 0.01 M, and
PCl 2 = 1.0 atm.

Basis: Half-reactions and standard reduction potentials given.

The half-reactions are already balanced as given in the problem. The spontaneous reaction under standard
o
+
conditions is 2 Ce 4(aq+ ) + 2 Cl (aq ) 2 Ce 3(aq
) + Cl 2 ( g ) ; the cell potential is = (1.700 1.358) V = 0.342 V.

Basis: [Ce4+] = 0.02 M, [Ce3+] = 2.0 M, [Cl-] = 0.01 M, and PCl 2 = 1.0 atm.
At 25.0oC, the cell potential is given by the Nernst Equation
=

R T
ln Qcell
n

or

0.0591597 V
log10 Q cell
n

For the cell at the given conditions,

[Ce ] P
=
[Ce ] [Cl ]
3+ 2

Q cell

4+ 2

Cl 2
2

2.02
0.02

1.0
1.0

= 108

Therefore
0.0591597 V
log10 Q cell
n
0.0591597 V
= 0.342 V
log10 10 8
2
= 0.10536 V

( )

The cell potential is 0.1054 V.

Electrochemistry Q4
Magnesium is produced commercially by the electrolysis of molten MgCl2. Calculate the mass of
magnesium metal that can be produced daily by the electrolysis of molten MgCl2 using an electrical
current of 100 kA. The electrolysis process has an efficiency of 77%.

Basis: One day of electrolysis operation.

The two half reactions are
Mg 2 + + 2 e Mg (s )
2 Cl Cl 2 ( g ) + 2 e

A line calculation gives

100000 A 1 day 86400 s
day

1 mol e96485.31 C

C
1 As

1 mol Mg
2 mol e-

24.305 g Mg
1 mol Mg

0.77

= 837.93 kg Mg

The daily production rate of Mg is 837.9 kg.

Electrochemistry Q5
Given that the standard reduction potential of oxygen gas at 25oC is
O 2 ( g ) + 4 H 3 O (+aq ) 6 H 2 O ( l )
= 1.229 V
calculate the equilibrium constant for the reaction
2 H 2(g ) + O 2 ( g ) 2 H 2 O (l )
o

at 25 C. Recall that the standard reduction potential of the hydronium ion is exactly 0.0 V.

Basis: Given the reduction half-reaction and potential for O2(g).

The two half-reactions are
O 2 ( g ) + 4 H 3 O (+aq ) + 4 e 6 H 2 O (l )
2 H 2 ( g ) + 4 H 2 O (l ) 4

H 3 O (+aq )

+4e

= 1.229 V
= 0.0 V

The overall equation is therefore

= 1.229 V

2 H 2 ( g ) + O 2( g ) 2 H 2 O (l )

At equilibrium, the Nernst equation gives

=

0.0591597 V
log10 K
n

The equilibrium constant for the formation reaction at 25oC is K = 1083.097 1.251083.
Electrochemistry Q6
Calculate the solubility of silver iodide (AgI) in water units of mol/L at 25oC using the following standard
reduction potentials:

Ag (+aq ) + e Ag (s )

AgI (s ) + e Ag (s ) +

I -(aq )

= 0.7996 V
= 0.15224 V

Basis: Given the half-reactions and standard reduction potentials.

For the overall dissociation reaction of AgI, the standard electropotential is
AgI (s ) Ag (+aq ) + I (-aq ) = (-0.15224-0.7996) V= -0.95184 V
When equilibrium is attained in a saturated AgI solution at 25oC, the Nernst equation gives
0.0591597 V
log10 K sp (AgI )
n

[ ][ ]

Substituting for the equation for the solubility product K sp (AgI ) = Ag + I = S 2 gives
= 0.0591597 V log10S2
S = 9.022657235 x 10-9 mol/L
Therefore the solubility of AgI in water is 9.02266 x 10-9 mol/L.
Kinetics Q1
Experiments were performed with different initial concentrations of A and B (no C) for the reaction
A + BC

The initial reaction rates were determined and are given in the following table.
exp't [A]0 [mol/L] [B]0 [mol/L] -(d[A]/dt)0 [mol/(L s)]
1
0.30
1.00
0.076
2
1.50
1.00
1.900
3
1.50
0.25
0.475
Determine the order of the reaction with respect to A and B and the value of the rate constant.

Basis: Given the concentration and reaction rate data.

By inspection of the rate data for experiments 1 and 2, the reaction rate increases by a factor of 25 when
the concentration of A is increased by a factor of 5. Also by inspection of the data for experiments 2 and
3, the reaction rate is directly proportional to the concentration of B. Therefore the reaction is second
order with respect to A and first order with respect to B. The reaction rate is given by

d [A]
= k [A ]2 [B]
dt

Using the experimental data we find that

k=

L2
d [A]

= 0.8444
mol 2 s
[B] dt 0

[A]2

The reaction rate constant is k = 0.844 L2/(mol2 s).

Kinetics Q2
The condensation of ethene (C2H4) to butene (C4H8) is given by the reaction

2 C 2 H 4 ( g ) C 4 H 8( g )
The concentration and rate data for this reaction under constant volume and constant temperature ( 500oC)
conditions are given in the following table.
0
384
1038
1977
3945
t [s]
[C2H4] [mol/L] 0.0162 0.0148 0.0129 0.0109 0.0082
Assuming that the reaction is irreversible at 500oC (i.e., KP is very large), determine the order of the
reaction with respect to the concentration of C2H4 and the rate constant at 500oC.
Basis: The given concentration and time data.
The rate of reaction is given by
rate =

1 d [C 2 H 4 ]

= k [C 2 H 4 ]n
2
dt

For various orders of reaction, the integrated rate laws are

ln
1

[C 2 H 4 ]
[C 2 H 4 ]0

[C 2 H 4 ]n 1 [C 2 H 4 ]0n 1

= 2 k t

= 2 (n 1) k t

k=

k=

[C 2 H 4 ]
1
ln
[C 2 H 4 ]0
2t

1
2 (n 1) t

for n = 1,

1
1
for n 1.

[C H ]n 1 [C H ]n 1
2 4 0
2 4

Assuming various orders of reaction with respect to C2H4 and calculating values of k using the above
expressions gives the following table of results
0
384
1038
1977
3945
t [s]
0.0148
0.0129
0.0109
0.0082
[C2H4] [mol/L] 0.0162
0.0
k(n=1) [s-1]
-1.1810-4 -1.1010-4 -1.0010-4 -8.6310-5
-1 -1
0.0
k(n=2) [Lmol s ]
7.6010-3
7.6110-3
7.5910-3
7.6310-3
2
-2 -1
-1
-1
-1
0.0
k(n=3) [L mol s ]
5.3010
5.8210
7.0110-1
4.9210
Only the assumption of a second-order reaction gives a consistent value of k over the entire time of
observation. Therefore the reaction is second-order with respect to C2H4 and the rate constant is k
7.60810-3 Lmol-1s-1.
Kinetics Q3
The gas phase reaction
AR +S

is assumed to be irreversible. Experimental data for the reaction rate at 375oC, starting with pure A is
given in the following table
0
100
500
1000
t [s]
Ptotal [atm] 0.10000 0.10909 0.13333 0.15000

Assuming that the reaction is not reversible at 375oC, determine the order of the rate of reaction with
respect to A and the specific reaction rate constant at 375oC in terms of partial pressure units.

Basis: The given concentration and time data.

At any instant, the partial pressure of R is equal to that of S. If the partial pressure of A decreases by an
amount x due to the reaction, the partial pressures of both R and S increase by the same amount (x). Thus,

x = Ptotal Pinitial
= PR = PS
Likewise, the partial pressure of A is
PA = Pinitial x

= 2 Pinitial Ptotal

For various orders of reaction, the integrated rate laws are

ln
1

[A]

n 1

[A]

n 1
0

[A]
[A]0

= k t

= (n 1) k t

[A]
1
k = ln
[A]0
t

k=

1
(n 1) t

1
1
n 1
[A ]
[A]0n 1

for n = 1,
for n 1.

Assuming various orders of reaction with respect to A and calculating values of k using the above
expressions gives the following table of results
0
100
500
1000
t [s]
0.1
0.1091
0.1333
0.150
Ptotal [atm]
0.0
0.0091
0.0333
0.050

PR=PS [atm]
0.1
0.0909
0.0667
0.050
PA [atm]
[A] [mol/L] 0.00188 0.0017093 0.0012535 0.0009401
0.0
k(n=1) [s-1]
9.53010-4 8.10810-4 6.93110-4
-1 -1
0.0
k(n=2) [Lmol s ]
5.31810-1 5.31810-1 5.31910-1
2
-2 -1
0.0
k(n=3) [L mol s ]
2.970102 3.535102 4.243102
Consistent values for k only occur for the second order reaction with respect to A.

Basis: Second order reaction with respect to A.

The average of the rate constant for the second order reaction is 5.31810-1 L/(mols). This can be
converted to the equivalent form in terms of pressure through the ideal gas law.
k
molK
5.31810-1 L
=
k =
= 9.99910-3 (atms)-1
mols
0.082058 Latm 648.15 K
R T
The rate constant in terms of the partial pressure is 1.0010-2 (atms)-1 with respect to A.

Kinetics Q4
The reaction rate of the dimerisation of chlorotrifluoroethane
2 C 2 F3 Cl ( g ) C 4 F6 Cl 2 ( g )

is found to be second order with respect to C2F3Cl. The reaction rate constant for this dimerisation was
determined at the following three temperatures.
523.5
498.2
473.0
T [K]
k [ L/(mols)] 2.11310-10 6.33910-11 1.68710-11
Calculate the activation energy for this reaction.

Basis: Given data for rate constant and temperature.

The Arrhenius equation
ln

k2
E
= a
k1
R

1
1


T2 T1

gives a linear relationship between the logarithm of the rate constant and the reciprocal of temperature.
-22

-22.5

ln k [-]

-23

y = -12394x + 1.3969
R2 = 1

-23.5

-24

-24.5

-25
0.0019

0.00195

0.002

0.00205

0.0021

0.00215

-1

1/T [K ]

Plotting ln k versus 1/T gives the following graph.

The slope of the fitted line passing through all three data points is Ea/R = 12394 K. Therefore the
activation energy for this reaction is Ea = 103.05 kJ/mol.

Kinetics Q5
The following data were obtained for the reaction A B. What is the order (n) and the rate constant (k)
in the rate law expression, rate = k [A]n ?
Experiment number

Initial [A],
molarity
0.20
0.40

1
2

Initial Rate, mol/L.s

0.75 x 10-5
3.0 x 10-5

Basis: Given experimental data.

Taking the ratios of the two experimental rates

R1 k [ A]1
=
R2 k [ A]2n
n

[ A]
= 1
[ A]2
0 .4
4=

0 .2

By inspection, the reaction is second order (n= 2).

At [A] = 0.2 M,
Rate

(0.2 mol)2
(L)2

0.75E-5 mol
Ls

The rate constant, k = 1.87510-4 L mol-1 s-1.

Kinetics Q6
Dinitrogen tetraoxide (N2O4) decomposes spontaneously at room temperature in the gas phase:
N 2 O 4 (g) 2 NO 2 (g)

The rate law governing the disappearance of N2O4 with time is

d [N 2 O 4 ]
= k [N 2 O 4 ]
dt

At 30C, k = 5.1106 s-1 and the activation energy for the reaction is 54.0 kJ/mol.
a) Calculate the time (in seconds) required for the partial pressure of N2O4(g) to decrease from 1 atm
to 0.11 atm at 30C.
b) Repeat the calculation of part (a) at 200C.

Basis: Partial pressures of N2O4(g); initial x0 = 1 atm, and final x = 0.11 atm.
From the rate law equation given above,

ln
ln

[N 2 O 4 ]
[N 2 O 4 ]0

= k t

0.11 atm
= t 5.1 10 6 s 1
1 atm
t = 4.327990026 10 7 s

The reaction takes place in 4.32810-7 s.

Basis: The same reaction as above at 300C.

The rate constant can be corrected for temperature using the equation from the Arrhenius expression

1 1

T2 T1

ln

E
k2
= a
k1
R

ln

k2
54000 J mol K
1
1

k1
8.3145 J mol 473.15 K 303.15 K
k2
= 2.202830372 10 3
k1
k 2 = 1.12444349 1010 s 1

The time for the reaction to occur can be calculated as above:

ln
ln

[N 2 O 4 ]
[N 2 O 4 ]0

= k t

0.11 atm
= t 1.12444349 1010 s 1
1 atm
t = 1.963008186 10 10 s

The reaction takes place in 1.96310-10 s.

Kinetics Q7
Write the rate law for the following reaction:
5 Br- (aq) + BrO3(aq) + 6 H+ (aq) 3 Br2 (l) + 3 H2O (l)
Data: the reaction proceeds by the following mechanism:

k1

BrO3 (aq ) + H + (aq )

HBrO3 (aq )
k 1

HBrO3 (aq )
BrO3 (aq ) + H + (aq )

Fast equilibrium

k2
+
HBrO3 (aq ) + H + (aq )
H 2 BrO3 (aq )
k 2
H 2 BrO3 (aq )
HBrO3 (aq ) + H + (aq )

Fast equilibrium

k3
+
Br (aq ) + H 2 BrO3 (aq )
( Br BrO2 )(aq ) + H 2 O (l )

Slow

k4
( Br BrO2 )(aq ) + 4 H + (aq ) + 4 Br
2 H 2 O + 3Br2

Fast

Basis: mechanism provided

The rate limiting step is:

k3
+
Br (aq ) + H 2 BrO3 (aq )
( Br BrO2 )(aq ) + H 2 O (l )
Therefore, the rate of reaction is:
+

r = k 3 [ Br ][ H 2 BrO3 ]

(1)

Use the second fast equilibrium to eliminate the intermediate H2BrO3+

+

k 2 [ HBrO3 ][ H + ] = k 2 [ H 2 BrO3 ]
+

[ H 2 BrO3 ] =

k2
[ HBrO3 ][ H + ]
k 2

(2)

Use the first fast equilibrium to eliminate the intermediate HBrO3:

k1[ BrO3 ][ H + ] = k 1[ HBrO3 ]

[ HBrO3 ] =

k1

[ BrO3 ][ H + ]
k 1

(3)

Combine Equations (2) and (3):

+

[ H 2 BrO3 ] =

k2
kk

[ HBrO3 ][ H + ] = 1 2 [ BrO3 ][ H + ]2
k 2
k 1k 2

(4)

Substitute Equation (4) into Equation (1) to obtain the final equation for the rate of reaction:
+

r = k 3 [ Br ][ H 2 BrO3 ] =

k1k 2 k 3

[ Br ][ BrO3 ][ H + ]2
k 1k 2

Notice that the last mechanism step is not required, since it is a fast reaction. This simply means that as
soon as the intermediate (Br-BrO2) is formed in the slop step, it immediately reacts with H+ according to
the mechanism of the fast step to produce H2O and Br2.