PRACTICE EXAM #1 (Ch. 14-15) : Rate K (S O) (I)

PRACTICE EXAM #1 (Ch.
14-15)
PAGE 1 of 3
Chem1B, General Chemistry II

1.) Peroxodisulfate (S2O82-) and iodide (I-) react according to the following balanced equation.
The data below was collected measuring the rate of the disappearance of S2O82- at 298 K.
S2O82-(aq) + 2 I-(aq) 2 SO42-(aq) + I2(aq)
Experiment [S2O82- ], initial [I- ], initial
1
0.010
1.0 10-4 M
-4
2
0.010
2.1 10 M
-4
3
0.0049
2.1 10 M
a.) Derive the complete rate law for the above reaction.
For S2O82-, use Exp. 1 and 2:
(
Rate, M/s
1.09
2.18
1.11
(0.476)x = 0.5 x = 1, first order in S2O82For I-, use Exp. 2 and 3:

(
(2.040)x = 1.963 x = 1, first order in I-
rate = k[S2O82- ][I- ]

b.) Calculate the average rate constant for all three trials, including units. Express it to
three significant figures.
For Exp. 1: 1.09 M/s = k (1.0 10-4 M)(0.010 M) k = 1.09 106 M-1 s-1
For Exp. 2: 2.18 M/s = k (2.1 10-4 M)(0.010 M) k = 1.038 106 M-1 s-1
For Exp. 3: 1.11 M/s = k (2.1 10-4 M)(0.0049 M) k = 1.078 106 M-1 s-1
Average: (1.09 106 M-1 s-1 + 1.038 106 M-1 s-1 + 1.078 106 M-1 s-1)/3
6
-1 -1
k = 1.068 106 1.07 10 M s
c.) Calculate the rate constant at 315 K, given that the activation energy for this reaction is
51.8 kJ/mol.
Use Arrheniuss Equation (ratio)
ln(k1/1.07 106) = - (51.8 103 J/mol)/(8.314 J/mol * K)[(1/315 K) (1/298 K)]
ln(k1/1.07 106) = (- 6230 K)(-0.0001811 K-1 )
ln(k1/1.07 106) = 1.128
(k1/1.07 106) = e1.128 = 3.090
6
-1 -1
k1 = (3.090)(1.07 106) = 3306874 3.31 10 M s
2.) Calculate the half life (t1/2) for a second-order reaction that has a rate constant of 3.18 10-4
M-2 s-1 and an initial concentration of 0.0561 M.
Use the half-life equation for the second order reaction.
4
t1/2 = 1/(k [A]0) = 1/(3.18 10-4 M-2 s-1 0.0561 M) = 1/(1.784 10-5) = 56054 5.61 10 s
PRACTICE EXAM #1 (Ch. 14-15)
PAGE 2 of 3

3.) Consider the following equilibrium.
CO(g) + 3 H2(g) CH4(g) + H2O(g)
H -230 kJ/mol, Kc = 190 at 1000 K
a.) At 1000 K, does the reaction favor reactants or products? Explain.
Products. Kc is larger than one (190 > 1), so the numerator ([products]) is larger.
b.) In which direction will this reaction shift (to reactants or to products) at 200 K? Explain.
Products. The negative enthalpy indicates that the reaction is exothermic; therefore,
heat is a product. Lowering the temperature will lower the heat, thus forcing the
equilibrium to favor the forward reaction to produce more.
c.) In which direction will this reaction shift (to reactants or products) if the volume of the
container is lowered? Explain.
Products. Lowering the volume will increase the pressure. There are four moles of gas
total on the reactants side and two on the products, the equilibrium will favor the
forward reaction to reduce the pressure.
d.) Calculate Kp for the above equilibrium.
Use Kp = Kc(RT)n
Kp = (190)[(0.0821 Latmmol-1 K-1)(1000 K)]-2
Kp = (190)(0.000148) = 0.028 0.03
4.) A 1.00 mole sample of NaHCO3(s) is put in an evacuated (empty) 2.50 L flask at 373.15 K.
Calculate the partial pressures of CO2(g) and H2O(g), in atm.
2 NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
Kp = 0.23
Kp = (PCO2)(PH2O), pure solids do NOT appear in the equilibrium constant expression.
Initial
Change
Equilibrium
0.23 = (x)(x)
3
79 0.48 atm
For CO2(g): 0.48 atm
For H2O(g): 0.48 atm
Total pressure: 0.48 atm + 0.48 atm = 0.96 atm
CO2
0
+x
x
H2O
0
+x
x
PRACTICE EXAM #1 (Ch. 14-15)
PAGE 3 of 3

5.) Consider the following equilibrium.
Ag+(aq) + Fe2+(aq) Ag(s) + Fe3+(aq)
Kc = 2.98
Initially, the solutions are prepared with excess Ag(s), [Ag+ ] = [Fe2+ ] = 0.200 M, and [Fe3+ ] =
0.350 M. Calculate the concentrations of each ion at equilibrium.
Calculate Q to compare to Kc.
Q=(
( 3
= 8.75 > Kc, therefore backwards reaction will occur.
)(
Ag+
0.200
+x
0.200 + x
Initial
Change
Equilibrium
2.98 = (
( 3 - )
)(
Fe2+
0.200
+x
0.200 + x
Fe3+
0.350
-x
0.350 - x
(2.98)(0.04 + 0.400x + x2) = 0.350 - x

2.98x2 + 1.192x + 0.1192 = 0.350 x
2.98x2 + 2.192x 0.2308= 0
x=
- ( )(
( )(
)(-
x = (-2.192 2.7488)/5.96, must be + to avoid negative concentration

x = (-2.192 + 2.7488)/5.96 = (0.5568)/6.06 = 0.09342
[Ag+ ] = 0.200 M + 0.09342 M = 0.293 M
[Fe2+ ] = 0.200 M + 0.09342 M = 0.293 M
[Fe3+] = 0.350 M 0.09342 M = 0.257 M
6.) The following reaction has an experimentally-derived rate law as given.
2 NO + 2 H2 N2 + 2 H2O
rate = k[NO]2[H2]
Show that this is consistent with the following three-step mechanism.

(1) 2 NO N2O2 (forward k1; backward k2), fast
(2) N2O2 + H2 N2O + H2O (k3), slow
(3) N2O + H2 N2 + H2O (k4), fast
Rate-determining step: N2O2 + H2 N2O + H2O, rate = k3[N2O2][H2]
From (1): k1[NO]2 = k2[N2O2], so [N2O2] = (k1[NO]2)/k2
Therefore,
rate = k3(k1[NO]2/k2)[H2] = (k3k1/k2)[NO]2[H2]

PRACTICE EXAM #1 (Ch. 14-15) : Rate K (S O) (I)

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PRACTICE EXAM #1 (Ch.

Chem1B, General Chemistry II

(0.476)x = 0.5 x = 1, first order in S2O82For I-, use Exp. 2 and 3:

(2.040)x = 1.963 x = 1, first order in I-

rate = k[S2O82- ][I- ]

PRACTICE EXAM #1 (Ch. 14-15)

Chem1B, General Chemistry II

H -230 kJ/mol, Kc = 190 at 1000 K

a.) At 1000 K, does the reaction favor reactants or products? Explain.

Kp = (PCO2)(PH2O), pure solids do NOT appear in the equilibrium constant expression.

PRACTICE EXAM #1 (Ch. 14-15)

Chem1B, General Chemistry II

= 8.75 > Kc, therefore backwards reaction will occur.

(2.98)(0.04 + 0.400x + x2) = 0.350 - x

x = (-2.192 2.7488)/5.96, must be + to avoid negative concentration

Show that this is consistent with the following three-step mechanism.

rate = k3(k1[NO]2/k2)[H2] = (k3k1/k2)[NO]2[H2]

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