3-Equilibrium-Activity_S11

Chemical Equilibrium- Activity Non-ideal Behavior of Ions and Molecules in Solution (SJ. 74) Equilibrium Many chemical reactions taking place in solution are reversible to some extent, and reaction takes place until a state of balance or chemical equilibrium is reached. If we are to introduce A and B into a suitable reactor and analyze the content of the reactor at time intervals, we would obtain a concentration versus time profile such as Figure 1.

Material A and B react to form products C and D aA + bB

cC

dD

where A, B, C, D = molecules or ions a, b, c, d = coefficients used to balance the equation In this reaction, a moles of A combines with b moles of B to form c moles of C and d moles of D.
A C B D Conc.

C D Time

A B

Equilibrium

Figure 1. Course of reaction between A, B, C, and D.

- The concentrations of A and B decrease until they reaches values that so not change with time, while the concentrations of C and D increase. - If the ratio of the concentration of products to reactants becomes constant, we say that the reaction is at equilibrium. 1

Equilibrium-Activity

Chemical Equilibrium (SJ, 58-60, chap 3.1-3.2) k1 aA + bB k2 k1 = rate constant for forward reaction k2 = rate constant for reverse reaction Rate of forward reaction, vf = k1 {A} a {B} b Rate of reverse reaction, vr = k2 {C} c {D} d Note { } = activity At equilibrium, vf = vr k1 {A} a {B} b = k2 {C} c {D} d k1 {C} c {D} d ---- = ---------------- = Keq {A} a {B} b k2 The ratio of products to reactants is constant. This phenomenon is known as chemical equilibrium. Such a law of nature is called the law of mass action or mass action law. cC + dD

The Law of Mass Action:

{Products} = {C} {D} K eq = {Reactants} { A}a {B}b

[C ] [ D ] = [ A] [ B ]
C D a A B

Keq = equilibrium constant or stability constant { } = activity [ ] = molar concentration (moles/L) mi = activity coefficient of species i Activity Coefficient, m

m = f (:) = f (I)
where : or I = ion strength or ionic strength

3-Equilibrium-Activity_S11

Ion strength or Ionic Strength, :

1 n = C i zi 2 2 i =1

by Lewis and Randall (1921)

where Ci = molar concentration of solute species i zi = charge or valence of solute species i n = number of solute species

Example 3-6 (SJ, p75): Compute the ionic strength of a solution containing the following concentration of ions: Ci (M) zi Ci zi 2 ----------------------------------------------------------------------------Cations -4 Ca 2+ 1x10 2 (1x10-4)(2)2 -3 Na+ 1.02 x10 1 (1.02x10-3)(1)2 Anions 1 x 10 2 (1.0x10-5)(2)2 CO3 -3 HCO3 1 x 10 1 (1.0x10-3)(1)2 2-4 1 x 10 2 (1.0x10-4)(2)2 SO4 ----------------------------------------------------------------------------3Ci zi 2 = 2.84 x 10-3
2-5

: = 3Ci zi 2 = 1.42 x 10-3

- : is often reported without stating units explicitly. Estimation of ionic strength Langelier (1936): : = (2.5 x 10 ) x (TDS in mg/L) -5 Russell (1976): : = (1.6 x 10 ) x (Specific Conductance in :mho/cm)
-5

Example 3-7 (SJ, p. 75) Which of the following brine has the greater ionic strength? Brine a: Brine b: 5,800 mg/L NaCl (5.8 g/L NaCl) 3,100 mgL MgSO4 (3.1 g/L MgSO4)

Equilibrium-Activity

(Solution) NaCl Na + + MgSO4 Mg2+ + Cl2SO4

For NaCl, 1) Calculate molecular weight: MW of NaCl = Na + Cl = 23 + 35.5 = 58.5 g/mole 2) Calculate molar concentration: 5.8 g mole M = ------- ----------- = 0.099 moles/L L 58.8 g 3) Calculate molar concentration for individual ion species: NaCl ----> 1M 0.099 4) Calculate ionic strength Na+ 1M 0.099 + Cl 1M 0.099
-

1 n Ci zi 2 = 0.5 [0.099 (1)2 + 0.099 (1)2] = 0.099 . 0.1 2 i =1

For MgSO4, 1) Calculate molecular weight: MW of MgSO4 = Mg +S + 4(O) = 24 + 32 + 4(16) = 120 g/mole 2) Calculate molar concentration: 3.1 g mole M = ------------ --------- = 0.0258 moles/L L 120 g 3) Calculate molar concentration for individual ion species: MgSO4 1M 0.0258 4) Calculate ionic strength ----> Mg 1M 0.0258
2+

SO4 1M 0.0258

2-

1 n Ci zi 2 = 0.5 [0.0258 (2)2 + 0.0258 (2)2 ] = 0.103 . 0.1 2 i =1

Note that they both have virtually the same ionic strength.

- Do Example 3-8 (SJ, p. 79)

3-Equilibrium-Activity_S11

Activity Coefficient, i
a) Debye-Hckel eqn:

log 10 i = 0 .5 ( z i ) 2

if : < 5 x 10

-3

(3-35; SJ, p. 77)

where mi = activity coefficient of solute species i b) The extended Debye-Hckel approximation Eqn

log 10 i =

A zi 2

( )

1 + ai B

if

: < 0.1

(3-35; SJ, p. 77)

where A, B, ai = coefficient (see F&C, p. 536 Appendix IV for their values) c) Gntelberg approximation (Debye-Hckel approximation Eqn at 15EC, a = 3 x 10 )
-8

log 10 i =

0 .5 z i 2 1+

(3-36; SJ, p. 79)

d) Use Fig 3.3 (F&C, p. 91) for rapid estimation of mi for common species. See p. 78 (SJ, p. 78) for the constants, A, B, and ai.

Equilibrium-Activity

Equilibrium constant needs to be adjusted when : is large.

{C} {D} K eq = a b { A} {B}

[C ] [ D ] = [ A] [ B ]
C D a A B A B

[C ] [ D ] a b [ A] [ B ]

( )( ) K ( )( )
C D

eq

= K eq c

K eq c = equilibrium constant adjusted for ionic strength

Example H2PO4+ 24

H+ 4

H+

HPO42-

Ka2

Ka2

{H }{HPO } = = {H PO }
2

+ 2 H HPO42- HPO 4 H PO - H 2 PO 4
2 4

If : = 0.01, T = 25EC; [H2PO4- ] = 9.698 x 10-5 M; [H+] = [HPO42-] = 3.018 x 10-6 M At 25C, A = 0.5085; B = 0.3281 x 108 H2PO4ai z 4.00 x 10-8 1 HPO424.00 x 10-8 2 H+ 9.00 x 10-8 1

Using the extended Debye-Hckel approximation Eqn. (: < 0.1 ) ,

log10 H

2 PO4

A zi 2

( )

1 + ai B

0.5085 12 1 + 4.00 x108

( ) 0.01 )( 0.3281x10 )
8

0.01

= 0.04495

H PO = 100.04495 = 0.90
2 4

3-Equilibrium-Activity_S11

Note:

Ka2

{H }{HPO } = = {H PO }
+ 24 2 4 c

H+

+ 2 H HPO42- HPO 4 H PO - H 2 PO 4
2 4

H PO H+ HPO 4 2- 2 4 = Ka2 = Ka2 H PO 2 4 + 2( ) HPO H

Ka 2 c is the ionic strength corrected Ka 2 pKa2c = log Ka2c

pKa2 = log Ka2

Example: Ammonium chloride, NH4Cl, is very soluble in water and NH4+ reaches equilibrium with NH3:
NH4Cl NH4+ NH4+ NH3
+ +

ClH+

A 0.01 M NH4Cl solution yields

C (M) NH3 NH4 H
+ +

2.371E-06 9.998E-03 2.371E-06 4.218E-09 1.000E-02

OH Cl
-

Using the extended Debye-Huckel approximation equation, determine the following (T = 25EC): a) the activity coefficients for NH4+, NH3, and H+ b) the equilibrium constant, Ka c) the equilibrium constant corrected for ionic strength, Kac d) pKa and pKac Note:

pKa = log Ka pKa c = log Ka c

Equilibrium-Activity

{H }{NH } = Ka = {NH }
+ 3 + 4

H+

+ H NH3 [ NH3 ] + NH + NH 4
4

+ NH + 4 H [ NH3 ] = + ( H + ) NH NH 4

Ka = Ka c

Solution
C (M) NH3
+ NH4

z 1 1 1 1
2 2

Cz

2.371E-06 9.998E-03 2.371E-06 4.218E-09 1.000E-02 9.998E-03 2.371E-06 4.218E-09 1.000E-02

+ -

OH Cl
-

C z = 2.000E-02 = (1/2) C z = 1.000E-02

log =

Az 2 1 + aB
8.974E-01 9.136E-01 9.003E-01 8.989E-01

a
+ NH4 +

z 1 1 1 1

A 0.5085 0.5085 0.5085 0.5085

B 3.2810E+07 3.2810E+07 3.2810E+07 3.2810E+07

-log -4.700E-02 -3.926E-02 -4.561E-02 -4.629E-02

2.500E-08 9.000E-08 3.500E-08 3.000E-08

OH Cl
-

C (M) NH3 {NH4 } {H } {OH } {Cl }

+ +

1 8.974E-01 9.136E-01 9.003E-01 8.989E-01

C 2.371E-06 8.973E-03 2.166E-06 3.797E-09 8.989E-03

Ka = pKa=
c c

2.37E-06 9.998E-03 2.371E-06 4.218E-09 1.000E-02

5.724E-10 9.24 5.623E-10 9.25

Ka=

p Ka=

3-Equilibrium-Activity_S11

{H }{NH } = Ka = {NH }
+ 3 + 4

H+

6 6 + H NH3 [ NH3 ] = 2.371x10 0.91 2.371x10 = 5.724 x1010 + NH + 0.897 9.998 x103 NH 4

) (

pKa = log Ka = log 5.724 x1010 = 9.24

+ NH + 4 H [ NH3 ] = + ( H + ) NH NH 4

Ka = Ka c =

( 0.897 ) 5.724 x1010 = 5.624 x1010 ( ) ( 0.913)(1)

pKa c = log Ka c = log 5.624 x10 10 = 9.25

Do Homework #3 (HW-3)