UNENE Chemistry Primer

UNENE Chemistry Primer
Lecture 13:
Chemical Equilibrium
Derek Lister and William Cook

University of New Brunswick
Course Textbook:
Chemistry, The Central Science, 10th edition, Pearson Education Inc., 2006
Theodore L. Brown, H. Eugene LeMay Jr. and Bruce E. Bursten
The Concept of Equilibrium
• Chemical equilibrium occurs when a reaction and its

reverse reaction proceed at the same rate.
• As a system approaches equilibrium, both the

forward and reverse reactions are occurring.
• At equilibrium, the forward and reverse reactions are

proceeding at the same rate.
Depicting Equilibrium
• Consider the reversible reaction between N2O4 and

NO2:
N2O4  2NO2
• In a system at equilibrium, both the forward and

reverse reactions are being carried out; as a result,
we write its equation with a double arrow.
A System at Equilibrium
• Once equilibrium is achieved, the amount of

each reactant and product remains constant.
The Equilibrium Constant
• Mathematically, the rate of a chemical reaction is described though its

rate law.
• For the forward reaction:
N2O4  2NO2
• The forward rate law is given as:
Where: kf is the rate constant

Rate = k f
[N
[N O ] is the concentration of N O2
O 4
]
2 4 2 4
• For the reverse reaction:
2NO2  N2O4
• And the rate law is:
Rate = k r [NO2 ]2
• Therefore, at equilibrium
Ratef = Rater
kf [N2O4] = kr [NO2]2
• Rewriting, it becomes:
2
kf [NO2 ]

kr [N2O4 ]
• The ratio of the rate constants is a constant, at that

temperature, thus:
kf [NO2 ]2
K eq  
kr [N2O4 ]
• Where Keq is the “Equilibrium Constant” for the

reversible reaction.
• To generalize this expression, consider the general

chemical reaction:
aA  bB  cC  dD
• The equilibrium expression for this reaction would be:
[C]c [D]d
Kc 
[A]a [B]b
• This is the generalized equilibrium constant based on
concentration of the components in the system.
• Because pressure is proportional to concentration for gases in a closed system,

the equilibrium expression can also be written as a pressure-dependent constant:
• Since, from the Ideal Gas Law: pCc pDd

Kp 
pAa pBb
PV  nRT
 
pi  ni V RT  c i RT
Relationship between Kc and Kp
• Plugging this into the expression for Kp for each substance, the relationship between Kc
and Kp becomes:
 
• Where: δn = (moles of product) – (moles of reactant) n
K p  K c RT
Equilibrium Can Be Reached from
Either Direction
• As you can see, the ratio of [NO2]2 to [N2O4] remains

constant at this temperature no matter what the initial
concentrations of NO2 and N2O4 are.
• It does not matter whether we start with N2 and H2 or
whether we start with NH3. We will have the same
proportions of all three substances at equilibrium.
What Does the Value of K Mean?
• If K >> 1, the reaction is product-favored; product

predominates at equilibrium.
• If K << 1, the reaction is reactant-favored; reactant

predominates at equilibrium.
The Concentrations of Solids and
Liquids Are Essentially Constant
• Both can be obtained by dividing the density of the

substance by its molar mass — and both of these are
constants at constant temperature.
• e.g., the concentration of water molecules can be

calculated as:
H O 1000 g/L
2
  55.6 mol/L
MwtH O 18 g/mol
2
The Concentrations of Solids and
Liquids Are Essentially Constant
• Therefore, the concentrations of solids and liquids do not appear in the equilibrium expression
– they are taken to have invariant concentrations or “activities” equal to unity (1):
• And:

PbCl2(s)  Pb(aq)
2
 2Cl (aq)
[Pb 2 ][Cl  ]2
Kc   [Pb 2 ][Cl  ]2
[PbCl2 ]
Equilibrium Calculations
• A closed system initially containing 0.001M H2 and 0.002 M
I2 is allowed to reach equilibrium at 448oC.
• Analysis of the equilibrium mixture shows that the

concentration of HI is 1.87 x 10−3 M.
• Calculate Kc at 448oC for the reaction taking place, which

is:
H2(g)  I2(g)  2HI(g)

What Do We Know?
[H2], M [I2], M [HI], M
Initially 1.000 x 10-3 2.000 x 10-3 0
Change
At 1.87 x 10-3
equilibrium
[HI] Increases by 1.87 x 10-3 M
[H2], M [I2], M [HI], M
Initially 1.000 x 10-3 2.000 x 10-3 0
Change +1.87 x 10-3
At 1.87 x 10-3
equilibrium
Stoichiometry tells us [H2] and [I2]
decrease by half as much …
[H2], M [I2], M [HI], M
Initially 1.000 x 10-3 2.000 x 10-3 0
Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3
At 1.87 x 10-3
equilibrium
We can now calculate the equilibrium
concentrations of all three compounds…
[H2], M [I2], M [HI], M
Initially 1.000 x 10-3 2.000 x 10-3 0
Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3
At 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

equilibrium
…and, therefore, the equilibrium
constant is calculated as:
 
2
3
[HI]2 1.87x10
Kc    51

[H2 ][I2 ] 6.5x10
5
1.065x10 
3
The Reaction Quotient (Q)
• To calculate Q, one substitutes the initial

concentrations on reactants and products into
the equilibrium expression.
[C]ci [D]di
Q
[A]ai [B]bi
• Q gives the same ratio the equilibrium
expression gives, but for a system that is not at
equilibrium.
aA  bB  cC  dD
• If Q = K, then the system is at equilibrium.
• If Q > K, there is too much product and the

equilibrium will shift to the left.
• If Q < K, there is too much reactant and the

equilibrium will shift to the right.
Le Châtelier’s Principle
“If a system at equilibrium is disturbed by a change

in temperature, pressure, or the concentration of
one of the components, the system will shift its
equilibrium position so as to counteract the effect
of the disturbance.”

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UNENE Chemistry Primer

Derek Lister and William Cook

• Chemical equilibrium occurs when a reaction and its

• As a system approaches equilibrium, both the

• At equilibrium, the forward and reverse reactions are

• Consider the reversible reaction between N2O4 and

• In a system at equilibrium, both the forward and

• Once equilibrium is achieved, the amount of

• Mathematically, the rate of a chemical reaction is described though its

• For the forward reaction:

Where: kf is the rate constant

• For the reverse reaction:

• And the rate law is:

• The ratio of the rate constants is a constant, at that

• Where Keq is the “Equilibrium Constant” for the

• To generalize this expression, consider the general

• The equilibrium expression for this reaction would be:

• Because pressure is proportional to concentration for gases in a closed system,

• Since, from the Ideal Gas Law: pCc pDd

• As you can see, the ratio of [NO2]2 to [N2O4] remains

• If K >> 1, the reaction is product-favored; product

• If K << 1, the reaction is reactant-favored; reactant

• Both can be obtained by dividing the density of the

• e.g., the concentration of water molecules can be

• Analysis of the equilibrium mixture shows that the

• Calculate Kc at 448oC for the reaction taking place, which

H2(g)  I2(g)  2HI(g)

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change +1.87 x 10-3

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

• To calculate Q, one substitutes the initial

• If Q = K, then the system is at equilibrium.

• If Q > K, there is too much product and the

• If Q < K, there is too much reactant and the

“If a system at equilibrium is disturbed by a change

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