CHEMICAL EQUILIBRIUM

condensed version
 The EQUILIBRIUM Condition

N2O4 2 NO2
colorless brown

Forward Reaction: N2O4 2 NO2 ratef = kf [N2O4]

Reverse Reaction: 2NO2 N2O4 rater = kr [NO2]2

At equilibrium, the rate at which NO2
forms in the forward reaction equals the
rate at which N2O4 forms in the reverse
reaction:
 The EQUILIBRIUM CONSTANT
For a general equilibrium equation:

aA +bB dD +eE
Products raised to
stoichiometric
powers…

…divided by reactants
raised to their
The EQUILIBRIUM CONSTANT stoichiometric powers
EXPRESSION
 The EQUILIBRIUM CONSTANT:
KC and KP
For a general equilibrium equation:

aA +bB dD +eE

When the reactants and products in a chemical

reaction are all gases, we can formulate the
equilibrium-constant expression in terms of
partial pressures.
Where p is pressure

Relating Kp and Kc :
 The EQUILIBRIUM CONSTANT
For a heterogeneous equilibria: (substances are in different phases)
Whenever a pure solid or a pure liquid is involved in a heterogeneous
equilibrium, its concentration is not included in the equilibrium-constant
expression.

PbCl2(s) Pb2+(aq) + Cl-(aq)

CaCO3(s) CaO(s) + CO2(g)

H2O(l) + CO32-(aq) OH-(aq) + HCO3-(aq)

Dependence of K on the Chemical Equation:
 Meaning of the equilibrium constant:
Magnitude of the equilibrium constant:

Kc >> 1 (large Kc)

 Reaction is strongly product favored.
 very little reactant remains
 often written as a forward reaction only.
 assume reaction goes to completion.
(large Kc)

Kc << 1 (small Kc)

 Reaction is strongly reactant favored.
 very little product forms
 usually written as “no reaction” or NR
(small Kc)
Write expressions for Kc, and KP if applicable, for the
following reversible reactions at equilibrium:

(a) HF(aq) + H2O(l) H3O+(aq) + F−(aq)

(b) 2NO(g) + O2(g) 2NO2(g)

(c) CH3COOH(aq) + C2H5OH(aq) CH3COOC2H5(aq) + H2O(l)

8
 Magnitude
Meaning ofof theequilibrium
the Equilibriumconstant:
Constant
The larger the value of the equilibrium
constant, Kc, the farther the reaction
proceeds to the right before reaching the
equilibrium state

Very small Very large

Reaction Reaction
proceeds hardly proceeds nearly
at all 10-3 103
to completion
1

Appreciable concentrations of both

reactants and products present at
equilibrium
 15.3
Methanol (CH3OH) is manufactured industrially by the reaction

CO(g) + 2H2(g) CH3OH(g)

The equilibrium constant (Kc) for the reaction is 10.5 at 220°C. What is the value of KP at this
temperature?

10
 15.3
Strategy

The relationship between Kc and KP is given by Equation (15.5). What is the change in the
number of moles of gases from reactants to product? Recall that

Δn = moles of gaseous products - moles of gaseous reactants

What unit of temperature should we use?

11
 15.3
Solution

The relationship between Kc and KP is

KP = Kc(0.0821T )Δn

Because T = 273 + 220 = 493 K and Δn = 1 - 3 = -2, we have

KP = (10.5) (0.0821 x 493)-2

= 6.41 x 10-3

12
y time
terms as molar concentrations, which are designated by squar
the cases you’ve seen so far, K is the equilibrium constant ba
PREDICTING THE from
tions, designated DIRECTION
now on as K OFc . REACTION:
Similarly, we designate
THE on
tient based REACTION
concentrationsQUOTIENT
as Qc . For the general balanced
aA bB BA cC dD
where a, b, c, and d area the
A stoichiometric
+bB c C + d the
coefficients, D rea
[C]c [D]d
Qc
[A]a [B]b
(Another form of the reaction quotientReaction
that we discuss later sh
quotient
tant and product terms as pressures.)
To construct the reaction quotient for any reaction, write t
If Q = Kof
tion first. For the formation c, the system isfrom
ammonia at equilibrium.
its elements, for
anced equation (with colored
If Q < Kc, coefficients fortoeasy
Q must increase reachreference)
equilibrium,i
the system3H
shifts forward. 2NH (g)
N2 (g) 2 (g) BA 3
If Q > Kc, Q must decrease to reach
To construct the reactionequilibrium,
quotient, the
we system
place shifts
the product term
backwards.
and the reactant terms in the denominator, multiplied by each ot
term to the power of its balancing coefficient (colored as in th
2
 ✓Check the sign of x, the
change in the concentr ation
S OLVING EQUILIBRIUM (or pressure)
Solving for x: At equilibrium,
How to solve equilibrium
PROBLEMS problems:
[CH
PRELIMINARY S ETTING UP S OLVING FOR x AND
So,
EQUILIBRIUM QUANTITIES
1. Write the balanced equation Thus,
2. Write the reaction quotient, Q 6. Substitute the quantities into Q
3. Convert all amounts into the [Hassume
7. To simplify the math, 2 S] 8.00
that M
correct units ( M or atm) x is negligible
([A]init – x = [A]eq [CS ] ) 4.00
» [A]2 init M
8. Solve for x
WORKING ON [H2 ] 8.00 M
THE REACTION TABLE ✓Check that assumption is
CHECK The comparison of Qc a
justified (<5% error). If not,
4. When reaction direction is not data
solvefrom partequation
(b) confirm thi
known, compare Q with K
5. Construct a reaction table
Apago PDF E
quadratic for x.
the reaction. Check that the co
9. Find the equilibrium quantities
(2.44) (1.76
✓Check the sign of x, the ✓Check to see that calculated
change in the concentr ation (5.56)(11.1
values give the known K
(or pressure)
FOLLOW-UP PROBLEM
phosphorus halides mixes 0.10
SAMPLE
toSOLUTIONPROBLEM
PLAN
solve for xCalculating
(the 17.7
To calculate
change Kc , we
in Calculating
need
[H ] BA]), and
theorequilibrium
[I Kconcentrations.
c from Concentration
substitute Wethe
2 Data
can concentrations
find the initial
2 [HI] into Qc
H2 and Atx from
mol
equilibrium,
the initial [HI]: 2
of amount
I2 form. 2
[HI](0.200 We setM.
0.078
mol) upCalculate
and a reaction
the flask K c.
volumetable,
(2.00use L), the known
and we [HI][HI]
are given at atequilibriu
SOL UTION Calculating
Inequilibrium
order tochange initial
studyc ,hydrogen [HI]: halide
PROBLEM
to solvePLAN
for xTo(the
calculate
(0.078KM). inFrom
we [H
need ] the
2 the or ]),decomposition,
[I2 0.200
equilibrium
balanced and mol
substitute
when 2x the
concentrations.
equation,
amol
researcher
We findfills
concentrations
of can
HI reacts,the an evacuated
into
initial
x mol Qc .
of [HI]
2.00-L flask [HI] 0.200 mol 0.100 M
SOLUTION Hwith
from
2
the 0.200
amount
Calculating
and x mol mol
of (0.200
initial
I 2
of
form. HI
mol)
[HI]:
We
[HI] gas
andupand
set the
a allows
flask
reaction
2.00 the
volume
table,
L reaction
(2.00
use
0.100 the L), to
andproceed
known
M [HI] at 453[HI]
we atareequilibrium
given C: at
equilibrium
to solve for(0.078
x (the M). From 0.2002.00
the] balanced L substitute
equation,
mol when 2x mol of HI intoreacts, x mol of
SettingH2up andthe
SOLUTION
x mol
change
of I2 form.
reaction
Calculating table,
in
2HI(g)
[HI]
[H
We with
initial
2
BAor [I 2 ]),
set upxa reaction
[HI]: 2.00
and
H[H
L
2 (g)] table,
2 or I[I
2 (g)
0.100
the
use
2 ] M
concentrations
the known
that forms [HI]
and
Q
at 2xc .
equilibrium[HI] tha
Setting to
upsolve
the forreaction table, with x [H
x (the change in [H2 ] or [I2 ]), 2and substitute ] or [I 2 ] that forms and 2x
the concentrations into Qc . [HI] that r
At equilibrium,
SOLUTION
[HI]Calculating
0.078initialM. Calculate
[HI]: 0.200Kmol c.
Setting up the reaction table, with x [HI] [H2 ] or [I0.100 2 ] thatM forms and 2x [HI] that react
PLAN To calculate Kc , we need the equilibrium 2.00 Lmol
0.200 concentrations. We can find the initial [HI]
[HI] 0.100 M
from the amount (0.200 mol) and the flask
Setting up the reaction table, with x [H2 ] or [I2 ] that 2.00volume
L (2.00
formsL),
andand2x we [HI]are
thatgiven
reacts: [HI] at
equilibrium (0.078
Setting up M).reaction
the
Concentration From(M)table,
the balanced x equation,
with 2HI( [H
) 2 ] orBA [I2 ]when 2x
H2 ( mol
that forms )and of
2x HI[HI]reacts,
) xreacts:
I2 ( that mol of
H2 and x mol ofInitial
I2 form. We set up a reaction table, use the known [HI] at equilibrium
to Solving
solve for x (the change in known [H2 ] or [HI] [I ]), andequilibrium:
substitute the concentrations into Qc .
Solving forforx,x,Change
usingthetheknown
using [HI]2 at at equilibrium:
SOLUTION Calculating initial [HI]: x
Solving for x, Equilibrium
using the known [HI] [HI] 0.100
[HI] at0.100
equilibrium:
M M 2x 2x x MM
0.078
0.078
0.200 mol
Solving for x, using the [HI]
[HI]
known x x[HI]0.100 MM M2x
at0.011
0.011 equilibrium: 0.100 0.078 M M
Solving for x, using the known 2.00 L
[HI] at equilibrium:
x 0.011
[HI] 0.100 M 2x 0.078 M
Therefore,
Therefore,thetheequilibrium
equilibriumconcentrations 0.100MMareare
concentrations
[HI] 2x 0.078 M
Setting up the reaction table,
Therefore, the equilibrium concentrations with x x [H
0.011 ]
2 Mor
are [I 2 ] that forms and 2x [HI] that reacts:
[H[H 2 ] 2 ] [I2[I ] 2 ] 0.011 x 0.011
M M and M
0.011 and [HI] [HI] 0.078 0.078MM
Therefore,
Therefore, thethe
[H equilibrium
2 ]equilibrium concentrations
[I2 ] concentrations
0.011 M are and
are [HI] 0.078 M
Substituting into the reaction quotient:
Apago
Apago PDF
PDF Enhanc
Enhance er r
Substituting into the[Hreaction
Substituting into the [H 2 ]2 ]
reaction
quotient:
[I[I2 2]quotient:
] 0.011
0.011 M M and
and2 ][I[HI]
[H [HI] 0.078
2] ]
0.078M M
Apago PDF Enhanc e r
Substituting
Substitutingintointothethereaction
reaction quotient: Qc [H2 ][I2 2]2 2
quotient: Qc [HI] 2
[H ][I
Apago
Apago PDF PDF Enhanc Enhanc Q c
(0.011)
Q
[H[HI]2e
[H2e][I
(0.011) r ]r
2 [HI]
][I 22 ]
Qc c
(0.011) (0.011)
2 2
Thus, Kc (0.011)(0.011) [HI]
[HI] 0.020
Thus,
Thus, K
Kc c (0.011) 0.078 2
(0.011) 2 0.0200.020
 Solve!
1. 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 900 K. What is the composition of the equililbrium
mixture? At this temperature, Kc is 1.56 for the equation:
CO(g) + H2O(g)  CO2(g) + H2(g)

2. Phosgene is a potent chemical warfare agent that is now outlawed

by internation 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] when each of the following amounts
of phosgene decomposes and reaches equilibrium in a 10.0 –L flask:
a) 5.00 mol of CoCl2 b) 0.100 mol of COCl2
Le Chatelier’s Principle
 Effects of various disturbances of a system at equilibrium
Ta b l e 1 7 . 4 Effects of Various Disturbances on a System at Equilibrium
Disturbance Net Direction of Reaction Effect on Value of K
Concentration
is Increase [reactant] Toward formation of product None
a Decrease [reactant] Toward formation of reactant None
a- Increase [product] Toward formation of reactant None
on Decrease [product] Toward formation of product None
ld Pressure
ut Increase P Toward formation of fewer moles None
he (decrease V ) of gas
of Decrease P Toward formation of more moles None
to (increase V ) of gas
h- Increase P None; concentrations unchanged None
of (add inert gas, no
m change in V )
ng Temperature
ly Increase T Toward absorption of heat Increases if H°r x n 0
If Decreases if H°r x n 0
ly Decrease T Toward release of heat Increases if H°r x n 0
we Decreases if H°r x n 0
Catalyst added None; forward and reverse None
equilibrium attained sooner;
rates increase equally
Consider the reaction:
N 2 O4 2 NO2 ΔH o = 58 kJ
Change SHIFT
Addition of N2O4(g) right
Addition of NO2(g) left
Removal of N2O4(g) left
Removal of NO2(g) right
Addition of He(g) none
Decrease in container volume left
Increase in container volume right
Increase in Temp right