Announcements

Hour Exam II
Thursday Feb 5, 2009
CTC 102 and 105
Time: 6:00 - 8:00 PM (1.5 hrs long)
Bring Blue Book, calculator and writing instrument.

Tomorrow, the “Zos-man” will go over selected problems

provided by all of the instructors. I think it will help.

Tomorrow we will review in class.

Equilibrium occurs when the rate of the forward
reaction and the rate of the reverse reaction are
equal!
kf Assume a reaction that is
A + 2B AB2 also an elementary reaction
kr

rateforward = kf [A][B]2 Because the reaction are

elementary we can write rate
ratereverse = kr [AB2] laws from balanced equation

ratef = rater At equilibrium the reactions

continue but at the same rate!
kf [A][B]2 = kr [AB2]

kf [AB2] Kc is defined as the ratio of the rate

= Kc = constants and is tied to stoichiometry
kr [A][B]2 of the elementary event!
The van’t Hoff Equation is the mathematical relationship
between the equilibrium constant and temperature.
R = universal gas constant
K2 ΔH0rxn 1 = 8.314 J/mol*K
1
ln = - - K1 is the equilibrium constant
K1 R T 2 T1
at T1 and K2 is the equilibrium
constant at T2
We have the Clausius-Clapyeron Equation, the Arrehenius Equation
and the van’t Hoff Equation

k2 Ea 1 1 P2 ΔHvap 1 1
ln = - - ln = - -
k1 R T2 T1 P1 R T2 T1

K2 ΔH0rxn 1 1
ln = - -
K1 R T2 T1
Stearic acid, nature's most common fatty acid, dimerizes
when dissolved in hexane:

2C17H35COOH <=> (C17H35COOH)2; ΔH°rxn = -172 kJ

The equilibrium constant for this reaction at 28°C is 2900.

Estimate the equilibrium constant at 38°C.

K2 ΔH0rxn 1 1
ln = - R T2
- T1
K1

R = universal gas constant K1 is the equilibrium

= 8.314 J/mol K constant at T1 and K2 is
the equilibrium constant at
T2
Solving Equilibrium Problems
• Two basic flavors of chemical equilibrium problems
1. Equilibrium quantities are given (concentrations or partial
pressures) and we solve for Kc. This is easy plug and chug.

2. We use ICE table to calculate either Kc from initial quantities

or we calculate equilibrium concentrations given Kc.
---it’s the algebra that’s tricky
In either case we can use a book-keeping technique
Initial, Change Equilibrium Method

Let’s try it in an example problem!

Calculating equilibrium concentration using a
simplfying assumption (no quadratic equation)
The reaction of nitrogen with oxygen giving nitrogen
oxide contributes to air pollution whenever a fuel is burnt
at high temperature. At 1500K the K = 1.0 X 10-5.
Suppose a sample of air has [N2] = 0.80 M, and [O2] =
0.20M before a reaction occurs. Calculate the
equilibrium concentrations at equilibrium.
N2(g) + O2(g) <==> 2NO(g) Kc = 1.0 X 10-5

PLAN:

Set up ICE table and begin filling it in.

1. Write down what we solve: Kc and what we know.
[NO]2
Kc = = 1.0 X 10-5
[N2] [O2]
2. Set up the ICE table
Molarity N2(g) + O2(g) <=> 2NO(g)
initial 0.80 0.20 0
+ change -x -x +2x
equilibrium 0.80 - x 0.20 - x 2x

3. Use equilibrium expression and substitute values. = 0.020

[NO]2 [2x]2
Kc = = 1.0 X 10-5 =
[N2] [O2] [.80 -x][.20 -x]
4. Either perfect square, quadratic equation or simplifying
assumption.
3. Use equilibrium expression and substitute values.
[NO]2 [2x]2
Kc = = 1.0 X 10-5 =
[N2] [O2] [.80 -x][.20 -x]
4. Either perfect square, quadratic equation or simplifying
assumption.
RULE: If 100 x K < [A]0 then .80 - x = .80
100 X 10-5 = 10-3 < [A]0 .......it’s ok to rid x.

[NO]2 [2x]2 [2x]2

Kc = = 1.0 X 10-5 = =
[N2] [O2] [.80] [.20] [.16]

(1.0 X 10-5 (.16))1/2 = 6.3 X 10-4

x=
( 4
[N2] = .80 - x = 0.80 - 6.3 X 10-4 = 0.80M
[O2] = -.20 - x = 0.20 - 6.3 X 10-4 = 0.20M
[NO] = 2x = 6.3 X 10-4 X 2 = 1.3 X 10-3M
Determining equilibrium concentrations from Kc
A chemical engineer mixes gaseous CH4 and H2O in
a 0.32 L flask at 1200 K. At equilibrium, the flask
contains 0.26 mol of CO, 0.091 mol of H2, and 0.041
mol of CH4. What is the [H2O] at equilibrium? A
Handbook states that Kc = 0.26 for this reaction is:
CH4(g) + H2O(g) CO(g) + 3H2(g) Kc = 0.26
PLAN: Use the balanced equation to write the Kc expression, and
then substitute values for each component.
[CO][H2 ]3
CH4(g) + H2O(g) CO(g) + 3H2(g) Kc =
[CH4 ][H2 O]

concentration (M) CH4(g) + H2O(g) CO(g) + 3H2(g)

initial ? ? ? ?
change ? ? ? ?
equilibrium 0.041 mol/0.32 L ? 0.26mol 0.091 mol
0.32 L 0.32 L
= 0.13 M
= 0.81 M = 0.28 M

[CO]eq[H2]eq3 (0.81)(0.28]3
[H2O]eq = = = 0.53 M
[CH4]eq Kc (0.13)(0.26]
Determining equilibrium concentrations from
initial concentrations and Kc
Fuel engineers use the extent of the change from CO and
H2O to CO2 and H2 to regulate the proportions of
synthetic fuel mixtures. If 0.250 mol of CO and 0.250 mol
of H2O are placed in a 125 mL flask at 900K, what is the
composition of the mixture at equilibrium? At 900K, Kc is
1.56 for this reaction.

CO(g) + H2O(g) CO2(g) + H2(g) Kc = 1.56

PLAN: 1)Balance equation, 2)write equilibrium expression, 3)

set up ICE table, 4)find the concentrations of all species
at initial conditions or equilibrium in the problem 5)use
algebra to determine equilibrium concentrations and then
substitute into a Kc expression.
Initial concentrations must be calculated as M, we have from the
data given [CO] = [H2O] = 0.250/0.125L = 2.00M.

concentration CO(g) + H2O(g) CO2(g) + H2(g)

_________________________________________________
initial 2.00 2.00 0 0
change -x -x +x +x
equilibrium 2.00 -x 2.00 -x x x

[CO2 ][H2 ] x2 x2
Kc = = = = 1.56
[CO][H2 O] (2.00 − x)(2.00 − x) (2.00 − x)2

x √
= 1.56 = ±1.25 (the negative result is ignored)
2.00 − x
x = 1.25(2.00 − x) = 2.50 − 1.25x
2.25x = 2.50
x = 1.11M = [CO2] = [H2] [CO] = [H2O] = 2.00 - x = 0.89 M
Same problem....but not a perfect square!
Fuel engineers use the extent of the change from CO
and H2O to CO2 and H2 to regulate the proportions of
synthetic fuel mixtures. If 0.250 mol of CO and 0.125
mol of H2O are placed in a 125 mL flask at 900K, what is
the composition of the mixture at equilibrium? At 900K,
Kc is 1.56 for this reaction.

CO(g) + H2O(g) CO2(g) + H2(g) Kc = 1.56

PLAN: 1)Balance equation, 2)write equilibrium expression, 3)

set up ICE table, 4)find the concentrations of all species
at initial conditions or equilibrium in the problem 5)use
algebra to determine equilibrium concentrations and then
substitute into a Kc expression.
Initial concentrations must be calculated as M, we have from the
data given [CO] = [H2O] = 0.250/0.125L = 2.00M.

concentration CO(g) + H2O(g) CO2(g) + H2(g)

_________________________________________________
initial 2.00 1.00 0 0
change -x -x +x +x
equilibrium 2.00 -x 1.00 -x x x

[CO2 ][H2 ] x2 x2
Kc = = = 2 = 1.56
[CO][H2 O] (2.00 − x)(1.00 − x) x − 3.00x + 2.00

x2 = 1.56(x2 − 3.00x + 2.00)

x2 = 1.56x2 − 4.68x + 3.12)
0.56x2 - 4.68x + 3.12 = 0 -b ± √b2 – 4ac
x=
2a

ax2 + bx + c =0
 [CO2 ][H2 ] x2 x2
Kc = = = 2 = 1.56
[CO][H2 O] (2.00 − x)(1.00 − x) x − 3.00x + 2.00

x2 = 1.56(x2 − 3.00x + 2.00)

x2 = 1.56x2 − 4.68x + 3.12)
0.56x2 - 4.68x + 3.12 = 0 -b ± √b2 – 4ac
x=
2a

ax2 + bx + c =0
- (-4.68 ± (-4.68)2 – 4(0.56)(3.12)
√
x=
2(0.56)
x = 7.6M and x = 0.73M
x = 7.6M makes 2.00 - x < 0 and makes no sense-toss it
x = 0.73 = [CO2] = [H2] and [CO] = [H2O] = 2.00 - 0.73
Using the Quadratic Formula
At 1280˚C the equilibrium constant (Kc) for the reaction
Br2 (g) 2Br (g) Kc is 1.1 X 10-3
is 1.1 x 10-3. If the initial concentrations are [Br2] =
0.063 M and [Br] = 0.012 M, calculate the
concentrations of these species at equilibrium.
1. Write Balanced Equation Br2 (g) 2Br (g)
[Br]2
2. Write Equilibrium Expression Kc =
[Br2]
3. Set Up ICE Table
Br2 (g) 2Br (g)
Let x
be the
Initial (M) [0.063] [0.012] change
Change (M) -x +2x in
concent
Equilibrium (M) 0.063 - x 0.012 + 2x
ration
[Br]2 (0.012 + 2x)2 of Br2
Kc = = Kc = = 1.1 x 10-3
[Br2] 0.063 - x

The expression is not a perfect square: we therefore must use

quadratic equation to solve it
 (0.012 + 2x)2
Kc = = 1.1 x 10-3
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
-b ± √b2 – 4ac
x=
2a
ax2 + bx + c =0
x = -0.0105 x = -0.00178

Br2 (g) 2Br (g)

Two solutions
Initial (M) [0.063] [0.012]
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

At equilibrium, [Br] = 0.012 + 2x = -0.009 M and 0.00844 M

At equilibrium, [Br2] = 0.062 – x = 0.06378 M
Phosgene is a potent chemical warfare agent that
is now outlawed by international agreement. It
decomposes by the reaction,

COCl2(g) CO(g) + Cl2(g) Kc = 8.3 x 10-4 (at 360 oC)

Calculate [CO], [Cl2], and [COCl2] at equilibrium when

the initial amount of phosgene gas is 0.100 mol in a
10.0 L flask.

[COCl2] = 0.100 mol/10.0 L = 0.0100 M

Kc = 8.3 x 10-4 (at 360 oC)

 [CO] [Cl2]
COCl2(g) CO(g) + Cl2(g) Kc = 8.3 x 10-4 =
[COCl2]

COCl2(g) CO(g) + Cl2(g)

Initial (M) 0.010 0.0 0.0
Change (M) -x +x +x
Equilibrium (M) 0.010 - x x x
(x) (x) x 2
Kc = 8.3 x 10-4 = =
(0.010 - x) (0.010 - x)
Kc = 8.3 x 10-4 (0.010 - x) = x2
Kc = 8.3 x 10-6 - 8.3 x 10-4 x = x2
Kc = 1x2 + 8.3 x 10-4 x - 8.3 x 10-6 = 0

ax2 + bx + c =0
 Kc = 1x2 + 8.3 x 10-4 x - 8.3 x 10-6 = 0

ax2 + bx + c =0 a=1
b = 8.3 x 10-4
-b ± √b2 – 4ac c = - 8.3 x 10-6
x= 2a

-8.3 x 10-4 ± √(8.3 x 10-4) 2 – 4(1) (-8.3 x 10-6)

x=
2(1)
x1 = 0.002495M = 0.0025M
x2 = -0.003325 which makes no sense and
rejected.

x = [CO] = [Cl2] = 2.5 x 10-3 M & 0.0100 - x = [COCl2] = 7.5 x 10-3 M.

The research and development unit of a chemical
company is studying the reaction of CH4 and H2S,
two components of natural gas.
CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00

mol of H2S and 2.00 mol of H2 are mixed in a 250 mL
vessel at 960 oC. At this temperature, Kc = 0.036.
(a) In which direction will the reaction proceed to
reach equilibrium?
(b) If [CH4] = 5.56 M at equilibrium, what are the
equilibrium concentrations of the other three substances?

PLAN: Find the initial molar concentrations of all components and use these to
calculate Qc. Compare Qc to Kc, determine in which direction the reaction
will progress, and draw up expressions for the equilibrium concentrations.
SOLUTION:

[CH4]initial = 1.00 mol/0.25 L = 4.00 M

[CS2]initial = 1.00 mol/0.25 L = 4.00 M
[H2S]initial = 2.00 mol/0.25 L = 8.00 M
[H2]initial = 2.00 mol/0.25 L = 8.00 M

[CS2][H2]4 =
[4.0][8.0]4
Qc = = 64.0
[CH4][H2 S]2 [4.0][8.0]2

Qc of 64 is >> than Kc = 0.036

The reaction will progress to the left.

CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

 SOLUTION:

concentrations CH4(g) + 2H2S(g) CS2(g) + 4H2(g)

______________________________________________________
initial 4.00 8.00 4.00 8.00
change +x + 2x -x - 4x
______________________________________________________
equilibrium 4.00 + x 8.00 + 2x 4.00 - x 8.00 - 4x
______________________________________________________

At equilibrium [CH4] = 5.56 M, so 5.56 = 4.00 + x; thus,

x = 1.56 M

[H2S] = 8.00 + 2x = 11.12 M

Therefore: [H2] = 8.00 - 4x = 1.76 M

[CS2] = 4.00 - x = 2.44 M