Beruflich Dokumente
Kultur Dokumente
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
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] 280 285 290 295 298.15
o
P [kPa] 0.9912 1.388 1.919 2.620 3.197
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
The number of moles of H2O evaporated is,
n = 0.105 g H2O mol H2O
H 2O = 0.0058284 mol H2O
18.01528 g H2O
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 H vap 1 1
ln 1o =
P R T T
2 1 2
Therefore,
1.5888 kPa 1 1
ln = (5354.734 K )
1.388 kPa Tdew point 285 K
Tdew point = 287.06 K
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
C2HCl3 32.05 0.243934 0.29999
CHCl3 67.95 0.569205 0.70001
Total 0.813139 1.00000
Basis: 100 g of solution containing 32.05 g of C2HCl3 and 67.95 g of CHCl3 at 25.0C.
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.
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
Since we know the mass of rhombic sulphur added, we can find the molecular weight of rhombic sulphur,
rS =
40.0 g rS
= 256.10533 g/mol rS
0.15619 mol rS
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.
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,
B
ln Pvap (mmHg ) = A
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.
2511.29
ln Pvap ,1 = 16.0828 = 531.12 mmHg
(25 + 273) 41.95
2511.29
ln Pvap , 2 = 16.0828 = 1080.93 mmHg
(45 + 273) 41.95
Use Clausius-Clapeyron equation to estimate Hvap:
Pvap , 2 H vap 1 1
ln =
Pvap ,1 R T1 T2
1
Pvap , 2 1 1 J 1080.93 1 1
1
kJ
H vap = R ln = 8.31451 ln = 27994.23
P T T mol.K 531.12 298 K 318 K mol
vap ,1 1 2
Phases Q7
From the freezing point depression we can calculate the effective molality of the solution.
T f 0.250oC mol mol
m eff = = o = 0.13441
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-
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).
CuSO 4 5H 2 O = 249.681
Mass dissolved at
- mass dissolved at end = mass precipitated
start
107.2 - 0.125 * ( 335 m) = 0.639 244 * m
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).
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 o
PH 2O = PH O
n + + n + nH O 2
Na Cl 2
0.25 mol + 0.25 mol
= 17.55 mm - Hg
0.25 mol + 0.25 mol + 55.50844 mol
= 0.15658 mm - Hg
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 o
PH 2O = PH O
n 2+ + n + nH O 2
Ca Cl 2
0.25 mol + 0.50 mol
= 17.55 mm - Hg
0 . 25 mol + 0 . 50 mol + 55 .50844 mol
= 0.23383 mm - Hg
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?
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?
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,
PC H x C H PCo H 0.57816 1.34 atm
y C6 H 6 = 6 6
= 6 6 6 6
= = 0.77474
Ptotal Ptotal 1 atm
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
1 1
H vap Po 1 200 mm - Hg
= ln 1o 1 = ln
1
1
= 4185.07 K
P
T
R 2 1 T2 400 mm - Hg 331.85 K 351.15 K
= 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
PC6 H14 x C6 H14 PCo6 H14 0.50091 101.325 kPa
y C6 H14 = = = = 0.72506
Ptotal Ptotal 70 kPa
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.
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
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?
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
Equilibrium Q1
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
K c = K P (R T ) n = = 31.9993 L/mol
atm mol K
Solving for x:
0.14865719128 extraneous root : causes (0.070 - x ) < 0
x=
- 0.01740650767
The concentration of R at equilibrium is (0.150+x) mol/L = 0.1326 mol/L.
Equilibrium Q2
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.
K c = K P (R T )
n
= 0.178571429 since n=0
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
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?
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
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.
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 P 2.0P
CO 0.0 +P P
H2 0.0 +P P
Equilibrium Q5
For reaction (1), since the change in the number of moles (n) is 1,
K c (1) = K P (1) (R T ) = 6.0932 0.0820578 atmL 500 K
= 249.997 mol/L
atm molK
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
Equilibrium Q6
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
2
= K sp (PbF )
2
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
2
= K sp (PbF )
2
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
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
4
)
dissociation of PbF2 and PbSO4 requires that
[ ][ ] = (0.5 n
Q PbF2 = Pb 2+ F
2
F
)( )
+ nSO 2 n F
4
2
= K sp (PbF ) = 3.7 10 8 mol 3 /L3
2
(1)
[ ][ ] ( )( )
QPbSO 4 = Pb 2+ SO 24 = 0.5 nF + nSO 2 nSO 2 = K sp (PbSO ) = 1.3 10 8 mol 2 /L2
4 4 4
(2)
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
Electrochemistry Q1
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?
Thus
1 hour 3600 s 100 A 1C 1 mol e- 1 mol Cl2 70.9054 g Cl2
1 = 132.279 g Cl2
1 hour 96485.31 C 2 mol e- 1 mole Cl2
As
Electrochemistry Q3
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.
Q cell =
[Ce ] P
3+ 2
Cl 2
=
2.02 1.0
= 108
[Ce ] [Cl ]
4+ 2 2 0.02 2
1.0 2
Therefore
0.0591597 V
= log10 Q cell
n
= 0.342 V
0.0591597 V
2
log10 10 8 ( )
= 0.10536 V
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%.
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 ) = 0.7996 V
AgI (s ) + e Ag (s ) + I -(aq ) = 0.15224 V
[ ][ ]
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
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.
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
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.
Assuming various orders of reaction with respect to C2H4 and calculating values of k using the above
expressions gives the following table of results
t [s] 0 384 1038 1977 3945
[C2H4] [mol/L] 0.0162 0.0148 0.0129 0.0109 0.0082
k(n=1) [s-1] 0.0 -1.1810-4 -1.1010-4 -1.0010-4 -8.6310-5
-1 -1
k(n=2) [Lmol s ] 0.0 7.6010-3 7.6110-3 7.5910-3 7.6310-3
2 -2 -1 -1 -1 -1
k(n=3) [L mol s ] 0.0 4.9210 5.3010 5.8210 7.0110-1
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
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
Assuming various orders of reaction with respect to A and calculating values of k using the above
expressions gives the following table of results
t [s] 0 100 500 1000
Ptotal [atm] 0.1 0.1091 0.1333 0.150
0.0 0.0091 0.0333 0.050
PR=PS [atm]
PA [atm] 0.1 0.0909 0.0667 0.050
[A] [mol/L] 0.00188 0.0017093 0.0012535 0.0009401
k(n=1) [s-1] 0.0 9.53010-4 8.10810-4 6.93110-4
-1 -1
k(n=2) [Lmol s ] 0.0 5.31810-1 5.31810-1 5.31910-1
2 -2 -1
k(n=3) [L mol s ] 0.0 2.970102 3.535102 4.243102
Consistent values for k only occur for the 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 5.31810-1 L molK
k = = = 9.99910-3 (atms)-1
R T mols 0.082058 Latm 648.15 K
The rate constant in terms of the partial pressure is 1.0010-2 (atms)-1 with respect to A.
Kinetics Q4
gives a linear relationship between the logarithm of the rate constant and the reciprocal of temperature.
-22
-22.5
-23
y = -12394x + 1.3969
ln k [-]
-23.5 R2 = 1
-24
-24.5
-25
0.0019 0.00195 0.002 0.00205 0.0021 0.00215
-1
1/T [K ]
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 ?
At [A] = 0.2 M,
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.
t = 4.327990026 10 7 s
The rate constant can be corrected for temperature using the equation from the Arrhenius expression
k2 E 1 1
ln = a
k1 R T2 T1
k2 54000 J mol K 1 1
ln =
k1 8.3145 J mol 473.15 K 303.15 K
k2
= 2.202830372 10 3
k1
k 2 = 1.12444349 1010 s 1
ln
[N 2 O 4 ] = k t
[N 2 O 4 ]0
0.11 atm
ln
1 atm
(
= t 1.12444349 1010 s 1 )
t = 1.963008186 10 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 )
Fast equilibrium
k 1
HBrO3 (aq ) BrO3 (aq ) + H + (aq )
k2 +
HBrO3 (aq ) + H + (aq ) H 2 BrO3 (aq )
Fast equilibrium
+ k 2
H 2 BrO3 (aq ) HBrO3 (aq ) + H + (aq )
+ 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 ]
+ k2 (2)
[ H 2 BrO3 ] = [ HBrO3 ][ H + ]
k 2
Use the first fast equilibrium to eliminate the intermediate HBrO3:
k1[ BrO3 ][ H + ] = k 1[ HBrO3 ]
k1 (3)
[ HBrO3 ] = [ BrO3 ][ H + ]
k 1
Combine Equations (2) and (3):
+ k2 kk
[ H 2 BrO3 ] = [ HBrO3 ][ H + ] = 1 2 [ BrO3 ][ H + ]2 (4)
k 2 k 1k 2
Substitute Equation (4) into Equation (1) to obtain the final equation for the rate of reaction:
+ k1k 2 k 3
r = k 3 [ Br ][ H 2 BrO3 ] = [ 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.