PHARMACEUTICAL CHEMISTRY 1 LECTURE: PRELIMS

CHEMICAL EQUILIBRIUM
- state where the concentration of the reactants and products remain constant with time
- dynamic situation (no net change)

LAW OF MASS REACTION
mA + nB oC + pD
rf [A][B] rf = Kf[A]
m
[B]
n
rf [C][D] rb = Kb[C]
o
[D]
p

rf = rb
Kf[A]
m
[B]
n
=

Kb[C]
o
[D]
p

APPLICATION:
1. N2 + 3H2 2NH3

2. 4NH3(g) + 7O2(g) 4NO2(g) + 6H2O(g)

Results of 3 Experiments for the reaction:
N2(g) + 3H2(g) 2NH3(g)
EXPT INITIAL CONCENTRATION EQUILIBRIUM CONCENTRATION
I
[N
2
]
O
= 1 M [N
2
] = 0.921 M
K =6.02 X 10 [H
2
]
O
= 1 M [H
2
] = 0. 763 M
[NH
3
]
O
= 0 [NH
3
] = 0.157 M
II
[N
2
]
O
= 0 [N
2
] = 0.399 M
K =6.02 X 10 [H
2
]
O
= 0 [H
2
] = 1. 197 M
[NH
3
]
O
= 1 M [NH
3
] = 0.203 M
III
[N
2
]
O
= 2 M [N
2
] = 2.59 M
K =6.02 X 10 [H
2
]
O
= 1 M [H
2
] = 2.77 M
[NH
3
]
O
= 3 M [NH
3
] = 1.82 M



EQUILIBRIUM EXPRESSIONS INVOLVING PRESSURES
N2 + 3H2 2NH3

APPLICATION:
2NO(g) + Cl2(g) 2NOCl(g)
PRESSURES AT EQUILIBRIUM
PNOCl 1.2 atm
PNO 5x10
-2
atm
PCl2 3x10
-1
atm

SOLUTION:

()

RELATIONSHIP BETWEEN Kc and Kp
Kp = Kc (RT)
n

()

R = 0.08206 T = K n = mole difference between products and reactants

EXAMPLE: Solve Kc if Kp = 1.9 x 10
-3

()

()()

Kc = 4.6 x 10
-4
HETEROGENOUES EQULIBRIA
Kc Kp
CaCo3(s) CaO(s) + CO2(g) CO2 PCO2
AgCl(s) Ag
+
(aq) + Cl
-
(aq) (Ag
+
)(Cl
-
) 0
P4(s) + 6Cl2(g) 4PCl3(g)
(

SOLID vs LIQUID GAS
Kc X
Kp X X

ASSIGNMENT:
A. Write the equilibrium expressions for Kc and Kp.
3O2(g) 2O3(g)
2ZnS(s) + 3O2(g) 2ZnO
(s)
+ 2SO
2(g)

2HgO(s) 2Hg(l) + O2(g)
B. Given: 2H2(g) + S2(g) = 2H2S(g)
0.208 M 1.125x10
-6
M 0.725 m
Solve for Kc and Kp at 700
o
C.
C. Given: N2(g) + O2(g) = 2NO(g)
0.15 atm 0.33 atm 0.50 atm
Solve for Kp and Kc at 2200
o
C.

------------------------------------------------------------------------------------------------------------------------------
Significance of the value of the equilibrium constant:
If K is < 1 (hence large), then the equilibrium lies to the right going to completion producing the
products.
If K is > 1 (hence small), then the equilibrium goes to the left hence the reaction does not occur to
any significant extent.
mA nB xC yD

Kc = 214 () Kc = 5.0x10
-4
()

For the reaction:
Kf N2O4 2NO2

Kc = 4.63x10
-3

Kb 2NO2 N2O4

a. N2(g) + 3H2(g) 2NH3(g)
b. N2(g) + 3/2H2(g) NH3(g)
c. 1/3 N2(g) + H2(g) 2/3NH3(g)
Give the relationship among the equilibrium constants.
Ka = Kb
2

Ka = Kc
3

Kb
2
= Kc
3

-------------------------------------------------------------------------------------------------------------------------
REACTION QUOTIENT (Q)
This uses equation using the initial concentration instead of the equilibrium constant.
If Q = Kc in equilibrium
If Q > Kc shift to the left
If Q < Kc shift to the right

Predict the direction where the equilibrium will shift of Kc = 6x10
-2
(right)
For the reaction: N2 + 3H2 = 2NH3
[NH3]o = 1 x 10
-3
M [N2]o = 1 x 10
-5
M

[H2]o = 2 x 10
-3
M
[NH3]o = 2 x 10
-4
M

[N2]o = 1 x 10
-5
M

[H2]o = 3.54 x 10
-1
M
[NH3]o = 1 x 10
-4
M

[N2]o = 5 M

[H2]o = 1 x 10
-2
M

a. Solve for Q

)(

) (

)(

)


(

()(

Backward Forward Forward




a. Consider the reaction: N2O4(g) 2NO2(g)
2.71 2x

If N2O4 is placed in a flask and allowed to reach equilibrium at a temperature where Kp = 0.133. At
equilibrium N2O4 is 2.71 atm. Calculate the equilibrium pressure of NO2.


(

()

------------------------------------------------------------------------------------------------------------------------------

b. Cis-stilbene trans-stilbene

Kc = 24 at 200
o
C If 0.850 M of cis-stilbene initially, calculate the equilibrium concentration of the 2
substances.

Cis-stilbene trans-stilbene
0.85 x x

x = 24(0.85 x)
x = 20.4 24x
25x = 20.4
x = 0.816 M trans-stilbene
0.85 0.816 = 0.034 M cis-stilbene




c. H2(g) + I2(g) 2HI(g)

Kc for the above reaction is 54.3; find the equilibrium concentration if the initial concentration of H2
and I2 are both 0.5 M.

H2 I2 HI
Initial 0.5 M 0.5 M 0
Change -x -x +2x
Equilibrium 0.5-x 0.5-x 2x


()

)(

)


()

( )( )

( )()



H2 = I2 = 0.107 M
HI = 0.786 M
------------------------------------------------------------------------------------------------------------------------------
ASSIGNMENT:
1. For the reaction:
CO2(g) + H2O(g) CO2(g) + H2(g)
If all reactant and products are 1 M, where will the equilibrium shift and what are the equilibrium
concentration of all the substances? Kc = 5.1
CO2(g) + H2O(g) CO2(g) + H2(g)
1 M 1 M 1 M 1 M
1 x 1 x 1 + x 1 + x

(

)(

)
()(

)

( )

( )

2.26 2.26x = 1 + x
x = 0.387 M
CO2 = H2O = 0.613 M
CO2 = H2 = 1.387 M



(

)(

)
()(

)


()()
()()

Q = 1
Q < Kc
The reaction will shift to the right.
-----------------------------------------------------------------------------------------------------------------------------
2. 2H2O 2H2 + O2
At equilibrium: 1.1x10
-1
M 1.9x10
-2
M ?
Kc = 2.4 x 10
-3

()
(

()
x = 0.08 M
O2 = 0.08 M


------------------------------------------------------------------------------------------------------------------------------

3. 2NO + Br2 2NOBr
? 0.159 atm 0.0768 atm
Kp = 109 at 25
o
C


(

)(

()

()()

69.324 x
2
= 5.89824x10
-3

x
2
= 8.508 x 10
-5

x = 9.22 x 10
-3
atm = PNO

4. H2 + I2 2HI
? ? 0.04 M
Kc = 54.3

()

)(

)



()

()()


54.3 x
2
= 2.95x10
-5

X = 5.43 x 10
-3
M = H2 = I2