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Chapter 6
Chapter 6
Source:
50 FACTS THAT SHOULD CHANGE THE WORLD
Jessica Williams, 2004, Icon Books Ltd.
CHEMICAL EQUILIBRIUM
A + B C + D
Example:
UV
CH4 + Cl2 CH3Cl + HCl
A B
reactant product
Forward reaction: reaction proceeds from
left to right
Backward reaction: reaction proceeds from
right to left
Reversible reaction: reactions which take
place in both forward and reverse directions
A B
reactant product
Two types:
physical equilibrium
chemical equilibrium
PHYSICAL EQUILIBRIUM
Physical change
H2O(l) H2O(g)
ratefwd = raterev
At equilibrium,
N2O4 molecules decompose
as fast as
NO2 molecules combine
N2O4(g) 2NO2(g)
A: Start
B: Mixture becomes pale brown
N2O4 decompose to reddish brown NO2
At equilibrium,
Rate of forward reaction: N2O4(g) 2NO2(g)
= Rate of reverse reaction: 2NO2(g) N2O4(g)
[N2O4(g)] and [NO2(g)] remain constant
But!
[N2O4(g)] [NO2(g)]
c) LAW OF CHEMICAL EQUILIBRIUM
aA + bB cC + dD
At equilibrium: [ C ]c [ D ]d = K
[ A ]a [ B ] b
Where:
a, b, c and d: stoichiometric coefficients for the reacting
species A, B, C and D
K = Equilibrium constant, [ ] = concentration
aA + bB cC + dD [C]c [D]d
K =
[A]a [B]b
REACTANTS PRODUCTS
By convention,
substances on the left reactants
substances on the right products
cC + dD aA + bB [A]a [B]b
K =
[C]c [D]d
REACTANTS PRODUCTS
EQUILIBRIUM CONSTANT (K)
N2O4(g) 2NO2(g)
[NO2]2
K=
[N2O4]
aA + bB cC + dD
[C]c [D]d
K =
[A]a [B]b
EQUILIBRIUM CONSTANT (K)
[C]c [D]d
aA + bB cC + dD K =
[A]a [B]b
Magnitude of K indicates how far a reaction proceeds
toward product at a given temperature.
[C]c [D]d
aA + bB cC + dD K =
[A]a [B]b
[C]c [D]d
aA + bB cC + dD K =
[A]a [B]b
Intermediate K At equilibrium:
significant amounts of both
reactant and product
equilibrium
equilibrium
equilibrium
Start with NO2 Start with N2O4 Start with NO2 & N2O4
[NO2 ]2 [NO2]2
K= = 4.63 x 10-3 The ratio [N O ] are constant
[N2O4] 2 4
K equilibrium constant
END OF
SLIDE SHOW
CHEMICAL EQUILIBRIUM
At constant temperature,
pressure is directly proportional to molar
concentration (n/V).
[NO2] (15.5)2
Kc = = = 6.44 x 105
[NO]2[O2] (0.0542)2 x 0.127
EXERCISE - 2
Consider the following equilibrium process at
700oC:
2H2(g) + S2(g) 2H2S(g)
Analysis shows that at equilibrium, there are
2.50 mol of H2,1.35 x 105 mol of S2, and
8.70 mol of H2S present in a 12.0L flask.
Calculate the equilibrium constant KC for
the reaction.
ANS:
1.08 x 107
EXERCISE - 3
At a certain temperature, KC = 1.8 x 104 for
the reaction
N2(g) + 3H2(g) 2NH3(g)
If the equilibrium concentrations of N2 and NH3
are 0.015 M and 2.00 M, respectively,
what is the equilibrium concentrations of H2?
ANS:
0.25 M
EXERCISE - 4
In a study of the conversion of methane to other
fuels, a chemical engineer mixes gaseous CH4
and H2O in a 0.32L 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 [H2O] at equilibrium?
KC = 0.26 for the equation
CH4(g) + H2O(g) CO(g) + 3H2(g)
ANS:
0.53 M
EXERCISE - 5
Equilibrium is established at 25oC in the
reaction
N2O4(g) 2NO2(g) KC = 4.61 x 103
If [NO2] = 0.0236 M in a 2.26L flask,
how many grams of N2O4 are also present?
ANS:
25.2 g
EXAMPLE - 2
The equilibrium constant Kp for the reaction
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure of
O2 if the PNO = 0.400 atm and PNO = 0.270 atm?
2
2
PNO PO 2
ANS: Kp = 2
PNO 2
2
PNO 2
PO 2 = Kp
2
PNO
1
2 N2O4(g) NO2(g) (at 25oC)
[NO2]
KC = = 0.0680
[N2O4]1/2
EXERCISE - 8
For the ammoniaformation reaction,
N2(g) + 3H2(g) 2NH3(g)
KC = 2.4 x 103 at 1000 K. If we change the
coefficients of this equation, what are the values
of KC for the following balanced equations?
1 N (g) + 3 H (g)
b) NH3(g)
2 2 2
2
EXERCISE - 9
At 25oC, KC = 7.0 x 1025 for the reaction:
2SO2(g) + O2(g) 2SO3(g)
What is the value of KC for the reaction:
1
SO3(g) SO2(g) + O2(g)
2
HETEROGENEOUS EQUILIBRIUM
Reactants and products are in different phases.
KC = [CO2] KP = PCO 2
PCO 2 = KP
[Ni(CO)4]
KC = P
[CO]4 KP = Ni(CO)4
P4
CO
EXERCISE - 10
Balance each of the following equations and
write its equilibrium constant expression,
KC and KP:
a) Na2O2(s) + CO2(g) Na2CO3(s) + O2(g)
b) H2O(l) H2O(g)
e) CO2(s) CO2(g)
c) N2O5(s) NO2(g) + O2(g)
EXAMPLE - 4 ANS:
PA = nA RT PB = nB RT PC = nC RT PD = nD RT
V V V V
= [A]RT = [B]RT = [C]RT = [D]RT
Derivation of equation: KP = KC(RT)n
PA = nA RT PB = nB RT PC = nC RT PD = nD RT
V V V V
= [A]RT = [B]RT = [C]RT = [D]RT
*Notice that, nA/V, nB/V, nC/V and nD/V have units mol L-1 and been
replaced by [A], [B], [C] and [D]
By substituting these relations into the expression of KP:
PCc PDd [C]c [D]d
KP = = x (RT)(c + d)(a + b)
PAa PBb [A]a [B]b
c d = KC(RT)n
= ([C]RT) x ([D]RT )
([A]RT)a x ([B]RTb) n = moles of gaseous products -
moles of gaseous reactants
Relationship between KP and KC can also be
written as KP = KC(0.0821T)n
R = 0.0821 L atm mol-1 K-1
If n = 0: KP = KC(0.0821T)0
KP = KC
KP = KC(RT)n
Hints:
aA(g) + bB(g) cC(g) + dD(g)
[C]c [D]d PCc PDd
KC = KP =
[A]a [B]b PAa PBb
PV = nRT
EXAMPLE - 5 ANS:
Two types:
Solve for KC or KP
[HI]2
KC =
[H2] [I2]
(0.160)2
=
0.020 x 0.020
= 64.0
EXAMPLE - 2
The atmospheric oxidation of nitric oxide,
2NO(g) + O2(g) 2NO2(g)
was studied at 184oC with pressure of 1.000 atm of
NO and 1.000 atm of O2.
At equilibrium, PO = 0.506 atm.
2
Calculate KP.
EXAMPLE - 2 ANS:
Change (atm) 2x x + 2x
Equilibrium (atm) 1.000 2x 1.000 x 0.000 + 2x
= 0.506 = 2x
So, x = 1.000 0.506
= 0.494
2
PNO 2
Kp = 2
PNO PO
2
(0.988)2
=
(0.012)2 x 0.506
= 1.34 x 104
EXAMPLE - 3
At 1280oC the equilibrium constant (Kc) for the
reaction
Br2(g) 2Br(g)
is 1.1 x 103. If the initial concentrations are [Br2] =
0.063 M and [Br] = 0.012 M, calculate the
concentrations of these species at equilibrium.
ANS: Let x be the change in concentration of Br2
Br2(g) 2Br(g)
Initial (M) 0.063 0.012
Change (M) x + 2x
Equilibrium (M) 0.063 x 0.012 + 2x
EXAMPLE - 8 ANS:
Br2(g) 2Br(g)
Initial (M) 0.063 0.012
Change (M) x + 2x
Equilibrium (M) 0.063 x 0.012 + 2x
Solve for x
EXAMPLE - 3 ANS:
Br2(g) 2Br(g)
Initial (M) 0.063 0.012
Change (M) x + 2x
Equilibrium (M) 0.063 x 0.012 + 2x
[Br2] = 0.0648 M
EXERCISE - 1
At particular temperature, suppose that the
initial temperatures of H2, I2, and HI are
0.00623 M, 0.00414 M and 0.0224 M.
H2(g) + I2(g) 2HI(g)
Calculate the concentrations of these species
([H2], [I2], [HI]) at equilibrium.
ANS:
[H2] = 0.00467 M
[I2] = 0.00258 M
[HI] = 0.0255 M
EXERCISE - 2
At 1280oC the equilibrium constant (KC) for
the reaction
Br2(g) 2Br(g)
is 1.1 x 103. If the initial concentrations are
[Br2] = 6.3 x 102 M and [Br] = 1.2 x 102 M.
Calculate the concentrations of these species
at equilibrium.
ANS:
[Br2] = 0.065 M
[Br] = 8.4 x 103 M
EXERCISE - 3
Consider the following equilibrium process at
686oC:
x
x 100 < 5% Assumption is OK
CHECK: [A]initial
5% rule
x Assumption is NOT OK
x 100 > 5%
[A]initial Use quadratic formula
EXAMPLE - 4 ANS:
[CO][Cl2] x2
KC = [COCl ] KC = = 8.3 x 104
2 (0.500 x)
Solve for x
EXAMPLE - 4 ANS:
[CO][Cl2]
KC = [COCl ] x2
2 KC = = 8.3 x 104
(0.500 x)
Solve for x
KC is very small
Assume x very small, 0.500 x 0.500
( x = 2.0 x 102 )
[CO][Cl2] x2
KC = [COCl ] KC = = 8.3 x 104
2 (0.010 x)
Solve for x
EXAMPLE - 4 ANS:
[CO][Cl2]
KC = [COCl ] x2
2 KC = = 8.3 x 104
(0.010 x)
Solve for x
Kc is very small
Assume x very small, 0.010 x 0.010
[CO][Cl2]
KC = [COCl ] x2
2 KC = = 8.3 x 104
(0.010 x)
Solve for x using quadratic formula
If incomplete = [ ]changes
X 100%
dissociation occurs: [ ]initial
THERMAL DISSOCIATION
N2O4(g) 2NO2(g)
Answer:
HCOOH(aq) H+(aq) + HCOO-
Initial [ ] 0.5 0 0
= [ ] changes
[ ] initial
= 8.9 x 10-3
0.5
= 0.02
EXAMPLE - 6
PNO22
KP =
PN2O4
0.2612
KP =
0.739
= 9.21 x 10-2 atm
ANS: EXAMPLE - 11
N2O4(g) 2NO2(g)
Initial (mol) 1 0
N2O4(g) 2NO2(g)
Initial (mol) 1 0
Changes -x +x
Equilibrium 1- x 2x
(mol)
ANS: EXAMPLE - 6
2x
PNO2 = (5 atm)
1 x + 2x
1x
PN2O4 = (5 atm)
1 x + 2x
ANS:
Kp = 2.9 x 104 Pa
END OF
SLIDE SHOW
CHEMICAL EQUILIBRIUM
To reach equilibrium, Q = K:
the products must increase, reactants decrease.
If Q < K, reactants products
To reach equilibrium, Q = K:
the products must decrease, reactants increase.
If Q > K, reactants products
N2O4(g) 2NO2(g)
ANS:
QP > KP
The reaction is not at equilibrium.
It will proceed to the left until QC = KC.
EXERCISE - 6
At 100oC, KP = 60.6 for the reaction
2NOBr(g) 2NO(g) + Br2(g)
In a given temperature, 0.10 atm of each
component is placed in a container.
Is the reaction at equilibrium?
If not, in which direction will it proceed?
ANS:
QP < KP
The reaction is not at equilibrium.
It will proceed to the right until QC = KC.
END OF
SLIDE SHOW
CHEMICAL EQUILIBRIUM
Add NH3
Original equilibrium: Q=K
[PCl5] increase
CHANGES IN PRESSURE (VOLUME)
[PCl5] decrease
Changes Shifts in the Equilibrium
Increase pressure Side with fewest moles of gas
I. At constant pressure
II. At constant volume
THE EFFECT OF THE ADDITION OF
INERT GAS ON EQUILIBRIUM
i) At constant pressure:
absorbed heat
Disturbance: rise in temperature
adds heat to the system
[PCl5]
KC =
[PCl3][Cl2]
[O2]
KC =
[SO2]
BUT, REMEMBER
Catalyst has no effect on the equilibrium
position and value of KC.
uncatalyzed catalyzed
uncatalyzed catalyzed
Change Equilibrium
Changes Shift Equilibrium Constant (value of K )
Concentration yes no
Pressure yes no
Volume yes no
Temperature yes yes
Catalyst no no
EXERCISE 13
Consider the following equilibrium process
between dinitrogen tetrafluoride (N2F4) and
nitrogen difluoride (NF2):
N2F4(g) 2NF2(g) H = 38.5 kJ
Predict the changes in equilibrium if
a) the reaction mixture is heated
b) NF2 gas is removed
c) the pressure decrease
d) inert gas, such as He, is added
EXERCISE - 14
Consider the equilibrium between molecular
oxygen and ozone
3O2(g) 2O3(g) H = 284kJ
What would be the effect of
a) increasing pressure by decreasing volume
b) increasing pressure by adding O2
c) decreasing the temperature
d) adding a catalyst
EXERCISE - 15
Heating solid sodium bicarbonate in a closed
vessel establishes the following equilibrium:
2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
What would happen to the equilibrium position if
a) some of the CO2 were removed
b) some solid Na2CO3 were removed
c) some solid NaHCO3 were removed
EXERCISE - 16
Consider the following equilibrium process:
PCl5(g) PCl3(s) + Cl2(g) H = 92.5 kJ
Predict the direction of the shift in equilibrium
when
a) the temperature is raised
b) more chlorine gas is added
c) some PCl3 is removed
d) pressure on the gases is increased
e) a catalyst is added to the reaction mixture
EXERCISE - 17
Consider the following equilibrium reaction in a
closed container:
CaCO3(s) CaO(s) + CO2(g)
What happen if
a) the volume is increased
b) some CaO is added
c) some CO2 is added
d) a few drops of a NaOH solution are added
e) a few drops of a HCl solution is added
f) temperature is increased
Note: Decomposition reactions are endothermic.
EXERCISE 18
Consider this equilibrium system
CO(g) + Fe3O4(s) CO2(g) + 3FeO(s)
How does the equilibrium position shift if:
a) CO is added
b) Solid NaOH is added
c) Fe3O4 is added
d) Dry ice is added at
constant temperature
Decrease [NH3]
Decrease volume (increase pressure)
Decrease temperature
Decrease [NH3]
Product: Ammonia
By removing ammonia, the system will
produce more in continual drive to reattain
equilibrium
The equilibrium will shift to the right
APPLICATION OF EQUILIBRIUM
PRINCIPLES IN THE HABER PROCESS
N2(s) + 3H2(g) 2NH3(g) H = 91.8 kJ
Decrease temperature
Formation of ammonia is
exothermic
Decreasing temperature
(removing heat) will shift the
equilibrium to the right
KC will increase
However, ammonia forms slowly at low temperature
that the process become uneconomical.