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Chapter 15:
Chemical Equilibrium

Chemistry: The Molecular Nature


of Matter, 6E
Jespersen/Brady/Hyslop

Dynamic Equilibrium in Chemical


Systems

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Chemical equilibrium exists when


Rates of forward and reverse reactions are equal
Reaction appears to stop
[reactants] and [products] don't change over
time
Remain constant
Both forward and reverse reaction never cease

Equilibrium signified by double arrows (


or equal sign (=)
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

Dynamic Equilibrium

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N2O4
2 NO2
Initially forward reaction rapid

As some reacts [N2O4] so rate forward

Initially Reverse reaction slow


No products

As NO2 forms

Reverse rate
Ions collide more frequently as [ions]

Eventually rateforward = ratereverse


Equilibrium
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

Dynamic Equilibrium

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(Fig. 15.1)

Almost all systems come to equilibrium


Where equilibrium lies depends on system
Some systems equilibrium hard to detect
Essentially no reactants or no products present
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

Reaction Reversibility

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Closed system
Equilibrium can be
reached from either
direction
Independent of whether
it starts with reactants
or products
Always have the same
composition at
equilibrium under same
conditions
Jespersen/Brady/Hyslop

N2O4

Chemistry: The Molecular Nature of Matter, 6E

2 NO2
5

Equilibrium

Products

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Reactants

N2O4

2 NO2

For given overall system composition


Always reach same equilibrium concentrations
Whether equilibrium is approached from forward or
reverse direction
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

Equilibrium

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Simple relationship among [reactants] and


[products] for any chemical system at
equilibrium
Called = mass action expression
Derived from thermodynamics

Forward reaction: A B
k
Reverse reaction: A B
A
B
At equilibrium:
kf

Rate = kf[A]
Rate = kr[B]
kf[A] = kr[B]

rate forward = rate reverse

rearranging:

Jespersen/Brady/Hyslop

[ B] k f
= =constant
[ A] kr
Chemistry: The Molecular Nature of Matter, 6E

Ex: H2(g) + I2(g)

2HI(g)

440C

Equilm
Amts
0.222 mol H2

Equilm
[M]
0.0222 M H2

10 L 1.00 mol I2

0.222 mol I2

0.0222 M I2

0.00 mol HI

1.56 mol HI

0.156 M HI

0.00 mol H2

0.350 mol H2

0.0350 M H2

10 L 0.100 mol I2

0.450 mol I2

0.0450 M I2

3.50 mol HI

2.80 mol HI

0.280 M HI

II

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Expt
Initial
Amts
#
I 1.00 mol H2

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

Ex: H2(g) + I2(g)

440C

Equilm
Amts

Equilm
[M]

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Expt Initial Amts


#

2HI(g)

III

0.0150 mol H2

0.150 mol H2

0.0150 M H2

10 L

0.00 mol I2

0.135 mol I2

0.0135 M I2

1.27 mol HI

1.00 mol HI

0.100 M HI

IV

0.00 mol H2

0.442 mol H2

0.0442 M H2

10 L

0.00 mol I2

0.442 mol I2

0.0442 M I2

4.00 mol HI

3.11 mol HI

0.311 M HI

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

Mass Action Expression (MAE)

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Uses stoichiometric coefficients as exponent


for each reactant
For reaction: aA + bB
cC + dD

[C ] c [ D ] d
Q=
[ A ] a [ B ]b

Reaction quotient

Numerical value of mass action expression


Equals Q at any time, and
Equals K only when reaction is known to be at
equilibrium
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

10

Mass Action Expression


2

= same for all data sets at equilibrium

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[ HI ]
Q=
[ H 2 ][ I 2 ]

Equilibrium Concentrations
(M)
Expt

[H2]

[I2]

[HI]

0.0222

0.0222

0.156

II

0.0350

0.0450

0.280

III

0.0150

0.0135

0.100

IV

0.0442

0.0442

0.311

[ HI ]
Q=
[ H 2 ][ I 2 ]
2

(0 . 156)
=49. 4
(0 . 0222)(0 . 0222)
2
(0 . 280 )
=49 .8
(0 . 0350)(0 . 0450 )
(0 . 100)2
=49. 4
(0 . 0150)(0 . 0135)
2
(0 . 311)
=49. 5
(0 . 0442)(0 . 0442)
Average = 49.5

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

11

Equilibrium Law

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For reaction at equilibrium write the following


Equilibrium Law
(at 440 C)
2

[ HI ]
K c=
=49. 5
[ H 2 ][ I 2 ]

Equilibrium constant = Kc = constant at given T


Use Kc since usually working with concentrations in
mol/L
For chemical equilibrium to exist in reaction
mixture, reaction quotient Q must be equal to
equilibrium constant, Kc
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

12

Predicting Equilibrium Law

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For general chemical reaction:


dD + eE
fF + gG

Where D, E, F, and G represent chemical formulas


d, e, f, and g are coefficients
f

Mass action expression =

[ F ] [G ]
d
e
[D] [E ]

Note: Exponents in mass action expression


are stoichiometric coefficients in balanced
f
g
equation.
[ F ] [G]
K c= d e
Equilibrium law is:

[ D] [ E]

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

13

Predicting Equilibrium Law

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Where only concentrations that satisfy this


equation are equilibrium concentrations
Numerator
Multiply [products] raised to their
stoichiometric coefficients
Denominator
Multiply [reactants] raised to their
stoichiometric coefficients
f

[ products ]
K c=
d
[ reactants ]
Jespersen/Brady/Hyslop

is scientists convention

Chemistry: The Molecular Nature of Matter, 6E

14

Ex. Equilibrium Law


2 NH3(g)

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3 H2(g) + N2(g)

Kc = 4.26 x 108 at 25 C
What is equilibrium law?

K c=

[ NH3 ]
3

[ H 2] [ N 2]

Jespersen/Brady/Hyslop

=4 . 2610

Chemistry: The Molecular Nature of Matter, 6E

15

Learning Check

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Write mass action expressions for the following:


N2O4 (g)
2 NO2 (g)

[ N 2O 4 ]
Q=
2
[ NO 2 ]
2CO (g) + O2 (g)

2 CO2 (g)

[CO 2 ]
Q=
2
[CO ] [O 2 ]
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

16

Your Turn!

A.
B.

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Which of the following is the correct mass


action expression (MAE) for the reaction:
Cu2+(aq) + 4NH3(aq)
[Cu(NH3)42+](aq)?
Q=
Q=

[Cu ( NH3 )2+


4 ]

[Cu 2+ ][ NH 3 ]4

[ Cu( NH3 )2+


4 ]
2+

[ Cu ][ NH3 ]
2+

[ Cu ][ NH 3 ]
C. Q =
2+
[ Cu( NH 3 )4 ]
D . none of these
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

17

Manipulating Equations for Chemical


Equilibria

A+B

C +D

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Various operations can be performed on


equilibrium expressions
1. When direction of equation is reversed,
new equilibrium constant is reciprocal of
original
C+D

A+B
Jespersen/Brady/Hyslop

[ C ][ D ]
K c=
[ A][ B ]

[ A][ B ] 1
K c=
=
[ C ][ D ] K c
'

Chemistry: The Molecular Nature of Matter, 6E

18

Ex. Manipulating Equilibria 1

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1. When direction of equation is reversed, new


equilibrium constant is reciprocal of original

3 H2(g) + N2(g)

K c=

[ NH3 ]
3

2 NH3(g)

at 25C

[ H 2] [ N 2]

=4 . 2610

2 NH3(g)
3 H2(g) + N2(g)
at 25C
3
[ H 2] [ N 2] 1
1
'
9
K c=
= =
=2 . 3510
2
8
K c 4 . 2610
[ NH3 ]
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

19

Manipulating Equilibria 2

A+B

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2. When coefficients in equation are


multiplied by a factor, equilibrium
constant is raised to a power equal to that
factor.

[ C ][ D ]
K c=
[ A][ B ]

C+D

3A + 3B
3

3C + 3D

[C ] [ D ] [C ][ D ] [ C ][ D ] [C ][ D ] 3
Kc= 3 3 =

=K c
[ A ] [ B ] [ A ][ B ] [ A][ B ] [ A][ B ]
''

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

20

Manipulating Equilibria 2

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2. When coefficients in equation are multiplied by


factor, equilibrium constant is raised to power
equal to that factor

3 H2(g) + N2(g) 2 NH3(g) at 25C

K c=

[ NH3 ]

[ H 2] [ N 2]

=4 . 2610

multiply by 3
9 H2(g) + 3 N2(g) 6 NH3(g)
6

[ NH 3 ]

''

Kc=

3
=K c
3

[ H 2 ]9 [ N 2 ]

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

21

Manipulating Equilibria 3

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3. When chemical equilibria are added,


their equilibrium constants are
multiplied
[
C
][
D
]
A+B
C+D
K =
c1

C+E

F+G

A+B+E

[ A][ B ]
[ F ][G ]
Kc =
2
[C ][ E ]

D+F+G

[ C ][ D ] [ F ][G ] [ D ][ F ][ G ]
Kc =

=
=K c K c
1
2
3
[ A][ B ] [C ][ E ] [ A ][ B ][ E ]
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

22

Manipulating Equilibria 3
2 NO2(g)

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3. When chemical equilibria are added, their


equilibrium constants are multiplied
NO3(g) + NO(g)

NO3(g) + CO(g)

NO2(g) + CO2(g)

NO2(g) + CO(g)

NO(g) + CO2(g)

Kc =

[ NO ][ NO3 ]
2

[ NO 2 ]
[ NO2 ][ CO 2 ]
Kc =
2
[ NO3 ][ CO ]
1

[ NO ][ CO 2 ]
Kc =
3
[ NO2 ][ CO ]

[ NO ][ CO 2 ]
[ NO ][ NO 3 ] [ NO2 ][CO 2 ]
=

[ NO2 ][ CO ]
[ NO 3 ][ CO ]
[ NO 2 ] 2
K c K c =K c
Therefore
1

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

23

Learning Check

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For: N2(g) + 3 H2(g)


2 NH3(g)
Kc = 500 at a particular temperature.
What would be Kc for following?
2 NH3(g)

N2(g) + 3 H2(g)
1
1
'
K c=
=
= 0.002
K c 500

N2(g) + 3/2 H2(g)


''

K c =K

1/ 2=

Jespersen/Brady/Hyslop

NH3(g)

500= 22.4

Chemistry: The Molecular Nature of Matter, 6E

24

Equilibrium Constant, Kc

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Constant value equal to ratio of product


concentrations to reactant concentrations
raised to their respective exponents
f

[ products ]
K c=
d
[ reactants ]

Changes with temperature (vant Hoff


Equation)
Depends on solution concentrations
Assumes reactants and products are in
solution
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

25

Equilibrium Constant, Kp

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Based on reactions in which substances are


gaseous
Assumes gas quantities are expressed in
atmospheres in mass action expression
Use partial pressures for each gas in place of
concentrations
Ex. N2 (g) + 3 H2 (g) 2 NH3 (g)
2

K P=

P NH 3

PN P
2

Jespersen/Brady/Hyslop

3
H

Chemistry: The Molecular Nature of Matter, 6E

26

How are Kp and Kc Related?

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Start with Ideal Gas Law


PV=nRT
Rearranging gives
n
P=
RT = MRT
V
Substituting P/RT for molar concentration
into Kc results in pressure-based formula

()

n = moles of gas in product moles of


gas in reactant
n

K p =K c ( RT )
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

27

Learning Check
N2O4(g)

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Consider the reaction: 2NO2(g)

If Kp = 0.480 for the reaction at 25C, what is


value of Kc at same temperature?
n = nproducts nreactants = 1 2 = 1

K p=K c (RT)

Kp
0 . 480
K c=
=
n
1
(RT)
(0 . 0821298 K )

Kc = 11.7

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

28

Your Turn!

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Consider the reaction A(g) + 2B(g)


4C(g)
If the Kc for the reaction is 0.99 at 25C, what
would be the Kp?
A. 0.99
B. 2.0
C. 24.
D. 2400
E. None of these

Jespersen/Brady/Hyslop

n=(4 3)=1

Kp = Kc(RT)n

Kp= 0.99*(0.082057*298.15)1
Kp = 24

Chemistry: The Molecular Nature of Matter, 6E

29

Homogeneous reaction/equilibrium

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All reactants and products in same phase


Can mix freely

Heterogeneous reaction/equilibrium

Reactants and products in different phases


Cant mix freely
Solutions are expressed in M
Gases are expressed in M
Governed by Kc

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

30

Heterogeneous Equilibria
Na2CO3(s) + H2O(g) + CO2(g)
[ Na2 CO 3 ( s ) ][ H 2 O ( g ) ][CO 2 ( g ) ]
Equilibrium Law =
K=
[ NaHCO 3 ( s) ] 2
Can write in simpler form
For any pure liquid or solid, ratio of moles to
volume of substance (M) is constant

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2NaHCO3(s)

Ex. 1 mol NaHCO3 occupies 38.9 cm3


2 mol NaHCO3 occupies 77.8 cm3
M=

M=

2 mol NaHCO3
0 . 0778 L

=25. 7M

1 mol NaHCO 3

=25 . 7M
0. 0389
L
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

31

Heterogeneous Equilibria
2NaHCO3(s)

Na2CO3(s) + H2O(g) + CO2(g)

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Ratio (n/V) or M of NaHCO3 is constant (25.7 mol/L)


regardless of sample size
Likewise can show that molar concentration of
Na2CO3 solid is constant regardless of sample size

So concentrations of pure solids and liquids


can be incorporated into equilibrium constant,
[ Na 2 CO 3 ( s) ]
Kc
K c=K
=[ H 2 O ( g ) ][ CO2 ( g ) ]
2
[ NaHCO 3 ( s ) ]
Equilibrium law for heterogeneous system written
without concentrations of pure solids or liquids
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

32

Learning Check

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Write equilibrium laws for the following:


Ag+(aq) + Cl(aq)
AgCl(s)
1
1
K c=
+
[ Ag
[ Ag ][Cl
] K =

H3PO4(aq) + H2O()

] [ Cl

H3O+(aq) + H2PO4(aq)
+

[ H 3 O ][ H 2 PO ]
K c=
[ H 3 PO 4 ]

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

33

Your Turn!
Ca3(PO4)2(s)

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Given the reaction:


3Ca2+(aq) + 2PO43(aq)

What is the mass action expression?


A.
B.
C.
D.

Q=

2
[Ca 2+ ]3 [ PO3
]
4

[Ca 3 ( PO 4 )2 ]

Q=

2
[Ca 2+ ]3 [PO 3
]
4

[1 ]
[ Ca 3 (PO4 )2 ]
Q = 2+ 3
2
[ Ca ] [ PO 3
]
4
[1 ]
Q = 2+ 3
3 2
[Ca ] [ PO 4 ]

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

34

Your Turn!
Ca3(PO4)2(s)

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Given the reaction:


3Ca2+(aq) + 2PO43(aq)

What is mass action expression for the reverse


2+ 3
3 2
[Ca
]
[
PO
reaction?
4 ]
A.

Q=

[Ca 3 ( PO 4 )2 ]
2+ 3

B.

C.

D.
Jespersen/Brady/Hyslop

Q=

[Ca ]

3 2
[PO 4 ]

[1 ]
[ Ca 3 (PO 4 )2 ]
Q = 2+ 3
2
[ Ca ] [ PO3
]
4
[1 ]
Q= 2+ 3
3 2
[Ca ] [ PO4 ]

Chemistry: The Molecular Nature of Matter, 6E

35

Interpreting KC

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Large K (K>>1)

Means product rich mixture


Reaction goes far toward
completion
Ex.
2SO2(g) + O2(g)

2SO3(g)

Kc = 7.0 1025 at 25 C

[ SO 3 ]

7 . 010
K c=
=
2
1
[ SO 2 ] [O 2 ]
Jespersen/Brady/Hyslop

25

Chemistry: The Molecular Nature of Matter, 6E

36

Interpreting KC

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Small K (K<<1)
Means reactant rich
mixture
Only very small amounts of
product formed
Ex.
H2(g) + Br2(g)

2HBr(g)

Kc = 1.4 1021 at 25 C
Jespersen/Brady/Hyslop

21

[ HBr ]
1 . 410
K c=
=
[ H 2 ][ Br 2 ]
1
Chemistry: The Molecular Nature of Matter, 6E

37

K 1

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Interpreting KC
Means product and
reactant concentrations
close to equal
Reaction goes only ~
halfway

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

38

K >> 1
K=1
K << 1

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Size of K gives measure of how


reaction proceeds

[products] >> [reactants]


[products] = [reactants]
[products] << [reactants]

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

39

Learning Check
N2O4(g)

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Consider the reaction of 2NO2(g)

If Kp = 0.480 at 25C, does the reaction favor


product or reactant?

K is small (K < 1)
Reaction favors reactant
Since K is close to 1, significant amounts of
both reactant and product are present
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

40

Equilibrium Positions and Shifts

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Equilibrium positions
Combination of concentrations that allow Q = K
Infinite number of possible equilibrium positions

Le Chteliers principle

System at equilibrium (Q = K) when upset by


disturbance (Q K) will shift to offset stress
System said to shift to right when
forward reaction is dominant (Q < K)
System said to shift to left when reverse
direction is dominant (Q > K)
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

41

Relationship Between Q and K


reaction at equilibrium
reactants products

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Q=K
Q<K

Too many reactants


Must convert some reactant to product to move
reaction toward equilibrium

Q>K

reactants products

Too many products


Must convert some product to reactant to move
reaction toward equilibrium
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

42

Examples of Le Chteliers Principle

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Lets see how this works with changes in


1. Concentration
2. Pressure and volume
3. Temperature
4. Catalysts
5. Adding inert gas to system at constant
volume

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

43

1. Effect of Change in Concentration


Cu(H2O)42+(aq) + 4Cl(aq)

yellow

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.

blue

CuCl42(aq) + 4H2O

Equilibrium mixture is blue-green


2
4
[CuCl 4 ( aq ) ][ H 2 O ]
K c=

4
[ Cu( H 2 O )2+
(
aq
)
][
Cl
(
aq
)
]
4
'

K c=

Kc

[ H 2O ]

[ CuCl4

( aq) ]

4
[ Cu( H 2 O )2+
(
aq
)
][Cl
(
aq
)
]
4

Add excess Cl (conc HCl)

Equilibrium shifts to products


Makes more yellow CuCl42
Solution
becomes Chemistry:
greenThe Molecular Nature of Matter, 6E
Jespersen/Brady/Hyslop

44

1. Effect of Change in Concentration


Cu(H2O)42+(aq) + 4Cl(aq)

yellow

2
[ CuCl 4 ( aq ) ]
K c=

4
[ Cu( H 2 O )2+
(
aq
)
][
Cl
(
aq
)
]
4

Add Ag+

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blue

CuCl42(aq) + 4H2O

Removes Cl:
Ag+(aq) + Cl(aq) AgCl(s)
Equilibrium shifts to reactants
Makes more blue Cu(H2O)42+
Solution becomes bluer

Add H2O?
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

45

Effect of Change in Concentration


2SO2(g) + O2(g) 2SO3(g)

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.

Kc = 2.4 x 10-3 at 700 oC


Which direction will the reaction move if
0.125 moles of O2 is added to an equilibrium
mixture ?
A. Towards the products
B. Towards the reactants
C. No change will occur

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

46

Effect of Change in Concentration

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When changing concentrations of reactants


or products
Equilibrium shifts to remove reactants or
products that have been added
Equilibrium shifts to replace reactants or
products that have been removed

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

47

Effect of Pressure and Volume Changes

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.

Consider gaseous system at constant T and n


2
2NH3(g)
3H2(g) + N2(g)
P NH
3
K P=
If reduce volume (V)
3

P N PH

2
Expect Pressure to increase (P)
To reduce pressure, look at each side of reaction
Which has less moles of gas
Reactants = 3 + 1 = 4 moles gas
Products = 2 moles gas
Reaction favors products (shifts to right)

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

48

Effect of P and V Changes

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Consider gaseous system at constant T and n


Ex.
H2(g) + I2(g)
2 HI(g)
2
P HI
K P=
P H PI 2
2
If pressure is increased, what is the effect on
equilibrium?
nreactant = 1 + 1 = 2
nproduct = 2
Predict no change or shift in equilibrium
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

49

Effect of P and V Changes


NaSO3(s) + H2O(g) + SO2(g)

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.

2NaHSO3(s)

K P =P H

P
O SO

If you decrease volume of reaction, what is


the effect on equilibrium?
Reactants: no moles gas = all solids
Products: 2 moles gas
V, causes P
Reaction shifts to left (reactants), as this has
fewer moles of gas
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

50

Effect of P and V Changes

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Reducing volume of gaseous reaction


mixture causes reaction to decrease number
of molecules of gas, if it can
Increasing pressure

Moderate pressure changes have negligible


effect on reactions involving only liquids
and/or solids
Substances are already almost incompressible

Changes in V, P and [X] effect position of


equilibrium (Q), but not K
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

51

Ice
water

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Effect of Change in Temperature

Cu(H2O)42+(aq) + 4Cl(aq)
blue

Boiling
water

CuCl42(aq) + 4H2O

yellow

Reaction endothermic
Adding heat shifts equilibrium toward products
Cooling shifts equilibrium toward reactants
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

52

Effect of Temperature Changes


H2O(s)

H =+6 kJ (at 0 C)

H2O()
H2O()

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Energy + H2O(s)

Energy is reactant
Add heat, shift reaction right

3H2(g) + N2(g)

3 H2(g) + N2(g)

2NH3(g) Hf= 47.19 kJ


2 NH3(g) + energy

Energy is product
Add heat, shift reaction left
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

53

Effect of Temperature Changes

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T shifts reaction in direction that produces


endothermic (heat absorbing) change
T shifts reaction in direction that produces
exothermic (heat releasing) change
Changes in T change value of mass action
expression at equilibrium, so K changed
K depends on T
T of exothermic reaction makes K smaller
More heat (product) forces equilibrium to reactants

T of endothermic reaction makes K larger


More heat (reactant) forces equilibrium to products
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

54

Catalysts And Equilibrium

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Catalyst lowers Ea
for both forward
and reverse
reaction
Change in Ea
affects rates kr
and kf equally

Catalysts have no
effect on
equilibrium
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

55

Inert gas

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Effect of Adding Inert Gas


One that does not react with components of
reaction
Ex. Argon, Helium, Neon, usually N2

Adding inert gas to reaction at fixed V (n and


T), P of all reactants and products
Since it doesnt react with anything
No change in concentrations of reactants or
products
No net effect on reaction
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

56

How to Use Le Chteliers Principle

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1. Write mass action expression for reaction


2. Examine relationship between affected
concentration and Q (direct or indirect)
3. Compare Q to K
If change makes Q > K, shifts Left
If change makes Q < K, shifts Right
If change has no effect on Q, no shift expected

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

57

Learning Check:

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Consider:
H3PO4(aq) + 3OH(aq)

3H2O() + PO43(aq)

3
[ PO 4 ]
Q=
3
[OH ] [ H 3 PO 4 ]

What will happen if PO43 is removed?


Q is proportional to [PO43 ]
[PO43 ], Q

Q < K equilibrium shifts to right


Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

58

Learning Check:
3H2O(aq) + PO43(aq)

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The reaction
H3PO4(aq) + 3OH(aq)

heat

is exothermic.
What will happen if system is cooled?
3
[ PO 4 ]
Q=
3
[OH ] [ H 3 PO 4 ]

Since reaction is exothermic, heat is product


Heat is directly proportional to Q
T, Q
Q < K equilibrium shifts to right
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

59

Your Turn!

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The equilibrium between aqueous cobalt ion


and the chlorine ion is shown:
[Co(H2O)6]2+(aq) + 4Cl(aq)
pink

[Co(Cl)4]2(aq) + 6H2O()

blue

It is noted that heating a pink sample causes it


to turn violet.
The reaction is:
A. endothermic
B. exothermic
C. cannot tell from the given
information
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

60

Your Turn!

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.

The following are equilibrium constants for the


reaction of acids in water, Ka. Which is the
most efficient reaction?
A. Ka = 2.2103
B. Ka = 1.8105

C. Ka = 4.01010
D. Ka = 6.3103

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

61

Equilibrium Calculations
For gaseous reactions, use either KP or KC

For solution reactions, must use KC

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Either way, two basic categories of


calculations
1. Calculate K from known equilibrium
concentrations or partial pressures
2. Calculate one or more equilibrium
concentrations or partial pressures using
known KP or KC

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

62

Calculating KC from Equilibrium


Concentrations

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.

When all concentrations at equilibrium are


known
Use mass action expression to relate
concentrations to KC
Two common types of calculations

A. Given equilibrium concentrations, calculate K


B. Given initial concentrations and one final
concentration
Calculate equilibrium concentration of
all other species
Then calculate K
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

63

Calculating KC Given Equilibrium


Concentrations
2NO2(g)

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Ex. 1 N2O4(g)

If you place 0.0350 mol N2O4 in 1 L flask at


equilibrium, what is KC?
[N2O4]eq = 0.0292 M

[NO2]eq = 0.0116 M
2
2
[ NO 2 ]
[ 0 . 0116 ]
K c=
K c=
[ N 2O4]
[ 0 . 0292]
KC = 4.61 103
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

64

Your Turn!

A. 14
B. 0.15
C. 1.5
D. 6.75

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For the reaction: 2A(aq) + B(aq)


3C(aq)
the equilibrium concentrations are: A = 2.0 M,
B = 1.0 M and C = 3.0 M. What is the
expected value of Kc at this temperature?
3

[C ]
K c= 2
[ A] [ B]

[ 3. 0 ]
K c=
2
[ 2 . 0 ] [1 . 0 ]

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

65

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.

Calculating KC Given Initial Concentrations


and One Final Concentration
Ex. 2 2SO2(g) + O2(g)
2SO3(g)
1.000 mol SO2 and 1.000 mol O2 are placed in
a 1.000 L flask at 1000 K. At equilibrium
0.925 mol SO3 has formed. Calculate KC for
this reaction.
1st calculate concentrations of each
Initial

1 .00 mol
[ SO 2 ]=[O 2 ]=
=1 .00 M
1. 00 L

Equilibrium

0 .925 mol
[ SO 3 ]=
=0 . 925 M
1 . 00 L

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

66

How to Solve:
Set up Concentration Table

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Based on the following:

Changes in concentration must be in same ratio


as coefficients of balanced equation
Set up table under balanced chemical equation

Initial concentrations

Controlled by person running experiment

Changes in concentrations

Controlled by stoichiometry of reaction

Equilibrium concentrations
Equilibrium
=
Concentration

Change in
Initial

Concentration
Concentratio
nChemistry: The Molecular Nature of Matter, 6E
Jespersen/Brady/Hyslop

67

Next Set up Concentration Table

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2SO2(g) + O2(g)

Initial Conc. (M)


1.000
Changes in Conc. (M) 0.925
Equilibrium Conc. (M) 0.075

1.000
0.462
0.538

2SO3(g)
0.000
+0.925
0.925

[SO2] consumed = Amt of SO3 formed


= [SO3] at equilibrium = 0.925 M
[O2] consumed = amt SO3 formed
= 0.925/2 = 0.462 M
[SO2] at equilibrium = 1.000 0.975 = 0.075
[O2] at equilibrium = 1.00 0.462 = 0.538 M
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

68

Ex. 2

K c=

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Finally calculate KC at 1000 K

[SO 3 ]

[ SO 2 ] [O 2 ]

[ 0. 925 ]
K c=
2
[ 0 . 075] [0 . 538 ]

Kc = 2.8 102 = 280

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

69

Summary of Concentration Table

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Used for most equilibrium calculations (Ch


15, 17, and 18)
1.Equilibrium concentrations are only values
used in mass action expression
Values in last row of table

1.Initial value in table must be in units of


mol/L (M)

[X]initial = those present when reaction prepared


No reaction occurs until everything is
mixed
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

70

Summary of Concentration Table

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3. Changes in concentrations always occur in


same ratio as coefficients in balanced
equation
4. In change row be sure all [reactants]
change in same directions and all [products]
change in opposite direction.

If [reactant]initial = 0, its change must be + ()


because [reactant]final negative

If [reactants] , all entries for reactants in change


row should have minus sign and all entries for
products should be positive
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

71

Calculate [X]equilibrium from Kc and [X]initial

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.

When all concentrations but one are known


Use mass action expression to relate Kc
and known concentrations to obtain
missing concentrations
Ex. 3 CH4(g) + H2O(g)
CO(g) + 3H2(g)
At 1500 C, Kc = 5.67. An equilibrium
mixture of gases had the following
concentrations: [CH4] = 0.400 M and
[H2] = 0.800M and [CO] =0.300M.
What is [H2O] at equilibrium ?
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

72

Calculate [X]equilibrium from Kc and [X]initial


Ex. 3 CH4(g) + H2O(g)

CO(g) + 3H2(g) Kc = 5.67

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[CH4] = 0.400 M; [H2] = 0.800M; [CO] =0.300M


What is [H2O] at equilibrium?
First, set up equilibrium
K c=

[ CO ][ H 2 ]

[ H 2 O ]=

[ CH 4 ][ H 2 O ]

[ CO][ H 2 ]
[CH 4 ] K c

Next, plug in equilibrium concentrations and Kc


3

[ 0. 300 ][0 . 800 ] 0 .154


[ H 2 O ]=
=
[ 0 . 400 ](5 . 67) 2 . 27
[H2O] = 0.0678 M
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

73

Calculating [X]Equilibrium from Kc

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.

When Initial Concentrations Are Given


Write equilibrium law/mass action expression
Set up Concentration table
Allow reaction to proceed as expected,
using x to represent change in
concentration
Substitute equilibrium terms from table into
mass action expression and solve

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

74

Calculate [X]equilibrium from [X]initial and KC


2HI(g) at 425 C

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Ex. 4 H2(g) + I2(g)

KC = 55.64

If one mole each of H2 and I2 are placed in a


0.500 L flask at 425 C, what are the
equilibrium concentrations of H2, I2 and HI?
Step 1. Write Equilibrium Law
2

[ HI ]
K c=
=55 . 64
[ H 2 ][ I 2 ]
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

75

Ex. 4 Step 2. Concentration Table


Initial
Change
Equilm

H2(g) +

I2(g)

2HI (g)

2.00
x
2.00 x

0.000
+2x
+2x

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Conc (M)

2.00
x
2.00 x

Initial [H2] = [I2] = 1.00 mol/0.500L =2.00M


Amt of H2 consumed = Amt of I2 consumed = x
Amt of HI formed = 2x
2

( 2x )
( 2x )
55 .64=
=
(2 . 00 x )(2 . 00 x ) (2 .00x )2
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

76

Ex. 4 Step 3. Solve for x

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Both sides are squared so we can take


square root of both sides to simplify

(2x )
K= 55 . 64=
2
(2 . 00 x )

2x
7 . 459=
(2. 00x )

7 . 459(2 . 00 x )=2x

14 .9187 . 459 x=2x

14 .918=9. 459 x

14 . 918
x=
=1 . 58
9. 459
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

77

Ex. 4 Step 4. Equilibrium Concentrations

Initial
Change
Equilm

H2(g) +

I2(g)

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Conc (M)

2.00
1.58
0.42

2.00
1.58
0.42

2HI (g)
0.00
+3.16
+3.16

[H2]equil = [I2]equil = 2.00 1.58 = 0.42 M


[HI]equil = 2x = 2(1.58) = 3.16

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

78

Calculate [X]equilibrium from [X]initial and KC


2HI(g) at 425 C

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Ex. 5 H2(g) + I2(g)

KC = 55.64

If one mole each of H2, I2 and HI are placed


in a 0.500 L flask at 425 C, what are the
equilibrium concentrations of H2, I2 and HI?
Now have product as well as reactants initially
Step 1. Write Equilibrium Law
2

[ HI ]
K c=
=55 . 64
[ H 2 ][ I 2 ]
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

79

Ex. 5 Step 2. Concentration Table


Initial
Change
Equilm

H2(g) +

I2(g)

2HI (g)

2.00
x
2.00 x

2.00
+2x
2.00 + 2x

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Conc (M)

2.00
x
2.00 x

(2 .00 +2x )2
(2 .00 +2x)2
55 .64=
=
(2 . 00 x )(2 . 00 x ) ( 2. 00x ) 2

(2 . 00+2x )
K= 55 . 64=
2
(2. 00x )
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

80

Ex. 5 Step 3. Solve for x

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.

2 . 00+2x
7 . 459=
(2. 00x )

7 . 459( 2 . 00 x )=2. 00+ 2x


14 .9187 . 459 x= 2. 00+ 2x
12. 918=9. 459 x

12 . 918
x=
=1 . 37
9. 459

Jespersen/Brady/Hyslop

[H2]equil = [I2]equil = 2.00 x =


2.00 1.37 = 0.63 M
[HI]equil = 2.00 + 2x
= 2.00 + 2(1.37)
= 2.00 + 2.74
= 4.74 M

Chemistry: The Molecular Nature of Matter, 6E

81

Your Turn!
N2(g) + O2(g)

2NO(g)

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Kc = 0.0123 at 3900 oC

If 0.25 moles of N2 and O2 are placed in a 250


mL container, what are the equilibrium
concentrations of all species ?
A. 0.0526 M, 0.947 M, 0.105 M
B. 0.947 M, 0.947 M, 0.105 M
C. 0.947 M 0.105 M, 0.0526 M
D. 0.105 M, 0.105 M, 0.947 M
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

82

Your Turn! - Solution


Conc (M)
Initial
Change
Equil

N2(g) +O2(g)

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2NO (g)

1.00
1.00
0.00
x
x
+ 2x
1.00 x 1.00 x
+ 2x
0.250 mol
[N2 ] = [O2 ] =
= 1.00M
0.250 L
(2x )2
2x
0.0123 =
0.0123 =
2
1 x
(1 x )
x = 0.0526M [NO] = 2x = 0.105M
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

83

Ex. 6

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Calculate [X]equilibrium from [X]initial and KC


CH3CO2H(aq) + C2H5OH(aq)
acetic acid

ethanol

CH3CO2C2H5(aq) +
ethyl acetate H2O(l)

KC = 0.11
An aqueous solution of ethanol and acetic
acid, each with initial concentration of 0.810
M, is heated at 100 C. What are the
concentrations of acetic acid, ethanol and
ethyl acetate at equilibrium?
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

84

Ex. 6 Step 1. Write Equilibrium Law


=0 . 11

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.

K c=

[ CH 3 CO 2 C 2 H 5 ]
[ C 2 H 5 OH ][CH 3 CO 2 H ]

Need to find equilibrium values that satisfy


this
Step 2: Set up concentration table using x
for unknown
Initial concentrations
Change in concentrations
Equilibrium concentrations
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

85

Ex. 6 Step 2. Concentration Table


I
C
E

0.810

C2H5OH(aq)

0.810

CH3CO2C2H5(aq) + H2O(l)

0.000

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(M) CH3CO2H(aq) +

x
0.810 x

x
0.810 x

+x
+x

Amt of CH3CO2H consumed = Amt of C2H5OH


consumed = x
Amt of CH3CO2C2H5 formed = + x
[CH3CO2H]eq and [C2H5OH ] = 0.810 x
[CH3CO2C2H5] = x

Jespersen/Brady/Hyslop

x
0 .11=
(0 .810x )(0. 810x )
Chemistry: The Molecular Nature of Matter, 6E

86

Ex. 6 Step 3. Solve for x

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Rearranging gives
2
0 .11(0 . 65611 . 62 x+ x )=x
Then put in form of quadratic equation
ax2 + bx + c = 0
2
0 . 072170. 1782 x +0 .11 x x=0
2
0 .11 x 1 . 1782 x+ 0. 07217=0
Solution for quadratic equation given by

b b 4 ac
x=
2a
2

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

87

Ex. 6 Step 3. Solve for x


(1. 1782)(1 . 1782) 4(0 .11 )(0 .07217 )
x=
2(0 . 11)

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1 .1782(1 . 388)(0 . 032) 1. 17821 .164


x=
=
0 . 22
0 . 22

This gives two roots: x = 10.6 and x =


0.064
Only x = 0.064 is possible
x = 10.6 is >> 0.810 initial concentrations
0.810 10.6 = negative concentration,
which is impossible
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Chemistry: The Molecular Nature of Matter, 6E

88

Ex. 6 Step 4. Equilibrium Concentrations


CH3CO2C2H5(aq) + H2O(l)

I
C
E

0.000
+0.064
+0.064

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(M) CH3CO2H(aq) + C2H5OH(aq)

0.810
0.064
0.746

0.810
0.064
0.746

[CH3CO2C2H5]equil = x = 0.064 M

[CH3CO2H]equil = [C2H5OH]equil = 0.810 M x


= 0.810 M 0.064 M
= 0.746 M

Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

89

Calculate [X]equilibrium from [X]initial and KC

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When KC is very small

2H2(g) + O2(g)

Ex. 7 2H2O(g)

At 1000 C, KC = 7.3 1018

If the initial H2O concentration is 0.100M,


what will the H2 concentration be at
equilibrium?
Step 1. Write Equilibrium Law
2

K c=

[ H 2 ] [O 2 ]
2

[ H 2O ]

Jespersen/Brady/Hyslop

=7. 310

18

Chemistry: The Molecular Nature of Matter, 6E

90

Ex. 7 Step 2. Concentration Table


Conc (M)

2H2O(g)

2H2(g) + O2(g)

18

7 .310

0.00
+2x
+2x

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Initial
0.100
2x
Change
Equilm 0.100 2x

0.00
+x
+x
3

(2x ) x
4x
=
=
2
2
(0 .1002x ) (0 . 1002x )

Cubic equation tough to solve


Make approximation

KC very small, so x will be very small


Assume we can neglect x
must prove valid later
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Chemistry: The Molecular Nature of Matter, 6E

91

Ex. 7 Step 3. Solve for x


Conc (M)
Initial
Change
Equilm

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Assume (0.100 2x) 0.100


2H2O (g)

2H2 (g) +

O2 (g)

0.100
2x
0.100

0.00
+2x
+2x

0.00
+x
+x

Now our equilibrium expression simplifies to


18

7 .310
3

(2x ) x
4x
=
=
2 0 . 010
(0 .100 )

4x =0 . 010(7 . 310
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18

) = 7.3 1020

Chemistry: The Molecular Nature of Matter, 6E

92

Ex. 7 Step 3. Solve for x


20

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7. 310
x =
=1 . 81020
4
Now take cubic root
3

x= 1 .810

20

=2 . 610

x is very small
0.100 2(2.6107) = 0.09999948
Which rounds to 0.100 (3 decimal places)
[H2] = 2x = 2(2.6107)
= 5.2107 M
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Chemistry: The Molecular Nature of Matter, 6E

93

Simplifications: When Can You


Ignore x in Binomial (Ci x)?

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If equilibrium law gives very complicated


mathematical problems
And if K is small
Change to reach equilibrium (x term) is also small
Compare initial concentration Ci in binomial to
Ci
value of K
> 400
K
Use proof to show that dropped x term was
sufficiently small
?

dropped x term
0 . 05
Ci

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Chemistry: The Molecular Nature of Matter, 6E

94

Learning Check

I
C
E

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For the reaction 2A(g) B(g)


given that Kp = 3.51016 at 25C, and we place 0.2
atm A into the container, what will be the pressure of B
at equilibrium?
2A
B
0.2
0 atm
+x
2x
0.2 2x 0.2
x

0
Q=
=0
2
(0 . 2)
Q<K shifts right

x = 1.41017

Q=
16

3 .510

PN
P

O4

2
NO

x
=
2
(0 . 2)

[B]= 1.41017 M

proof: 1.41017/0.2<0.05

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Chemistry: The Molecular Nature of Matter, 6E

95

Your Turn!

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In the reaction shown, K = 1.8 105


HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2(aq)
If we start with 0.3M HC2H3O2, what will be the
equilibrium concentration of C2H3O2 ?
A.
B.
C.
D.

0.3 M
0.002 M
0.04 M
0.5 M

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Chemistry: The Molecular Nature of Matter, 6E

96

Calculating KC Given Initial Concentrations


and One Final Concentration

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Ex. 2a
H2(g) + I2(g) 2HI(g) @ 450 C
Initially H2 and I2 concentrations are 0.200
mol each in 2.00L (= 0.100M); no HI is
present
At equilibrium, HI concentration is 0.160 M
Calculate KC
To do this we need to know 3 sets of
concentrations: initial, change and
equilibrium
Jespersen/Brady/Hyslop

Chemistry: The Molecular Nature of Matter, 6E

97

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