Equilibrium Calculations

Chemical Equilibrium - a review or introduction

Energy drives the chemical reactions. At some point, a reaction can go in either direction. A system at this condition is said to be at equilibrium. For chemical equilibrium, let us consider a general chemical reaction of the type: a A + b B -> a C + d D where A, B - represent reactants C, D - represent products a, b, c, d - coefficients of a balanced chemical equation. If the system is at equilibrium at a given temperature, then the following ratio is a constant.
[C]c [D]d ---------------[A] a [B] b

Keq

The square brackets "[ ]" around the chemical species represent their concentrations. This is the ideal law of chemical equilibrium or law of mass action. The unit for K depends on the units used for concentration. If M is used for all concentrations, K has a unit of Mc+d-(a+b) On the other hand, the units are not emphasized for equilibrium constant, and we often do not worry about the units. The equilibrium constants are used for energy calculation. They are thermodynamic properties of chemical reactions. In those calculations, the units of K and units of R (the gas constant) must match. So, some people even considers K a unitless number. If the system is not at equilibrium, the ratio may be different from the equilibrium constant. In such cases, the quotient is designated as Q.
[C]c [D]d ---------------[A]a [B]b = Q

A system will change in such a way that Q approaches the equilibrium constant Keq.

Applications or Examples

1.

You should be able to write the equilibrium expression for any reaction. As an example, the equilibrium constant for the reaction: + NH3 + HOAc = NH4 + OAc

is
+ [NH4 ] [OAc ] --------------------[NH3] [HOAc] = K

2.

For the ionization of an acid, + 2H2SO4 = 2 H + SO4

the equilibrium constant may be written as

+ 2 [H ] [SO4 2] = K

------------------[H2SO4]

3.

For the reaction: 2+ 2+ Cu + 6 NH3 = Cu(NH3)6

The equilibrium constant is expressed as

[Cu(NH3)6 2+ ] = K

----------------2+ 6 [Cu ] [NH3]

The equilibrium constant depends on the written formula.

4.

The ionization of oxalic acid, H2C2O4, has two stages:

Experimentally, it has been shown that + H2C2O4 = H + HC2O4 - - - - - - - - - (1)

+ [HC2O4 ] [H ] ------------------[H2C2O4] = K1 = 0.059

The second ionization constant is much smaller:

+ 2HC2O4 = H + C2O4 - - - - - - - - - (2)

+ [H ] [C2O4 2] = K2 = 0.000064

-------------------[HC2O4 ]

The overall ionization can be obtained by adding (1) and (2) to give (3). + 2H2C2O4 = 2 H + C2O4 - - - - - - - - - (3)

and the equilibrium constant is

+ 2 [H ] [C2O4 2] = K3

--------------------[H2C2O4]

It is obvious that
K3 = K1 * K2

= 3.8E(-6)

You should confirm the above obvious relationship to satisfy yourself. There are questions in the dialogue for practice.

In the DOS version, you press the (Q) key to enter the quiz mode.

Confidence Building Questions

1.

If the equilibrium constant for the reaction HCOOH + CN = HCN + HCOO

is 5e5, what is the equilibrium constant for the reaction HCN + HCOO = HCOOH + CN ?

Hint... Since the reaction is reversed, use the relationship K(reverse) = 1/K(forward). Try 2e-6, or 0.2e-5.

Answer 2e-6 Consider... 1/(5e5) = 2e-6.

2.

For reactions taking place in gas phase, the equilibrium constant is usually expressed in partial pressures of the reactants and products. If C represents the concentration, and other symbols of the ideal gas equations (P V = nR T) are used, which of the following is correct? (a) C = RT/(PV) (b) C = RT/P (c) C = RT/V (d) C = RT/(PM) (e) C = P/(RT) (f) C = PV/(RT)

Hint... C = (n/V) by definition. n R T = P V

Answer e Consider... C = (n/V) = P/(RT) P/(RT) = n/V = C which is concentration, by definition.

3.

If Kc represents the equilibrium constant of concentration, and Kp represents that of partial pressure, which one of the following is correct? (a) Kc = Kp (b) Kc is proportional to Kp (c) Kc = 1/Kp (d) Kc is inversely proportional to Kp (e) Kc * Kp = RT

Hint... Reason with yourself before answer. Statement (c), (d), and (e) may be true for special cases, but they are not generally true.

Answer b Consider... For a general case, Kc is proportional to Kp.

4.

For which two of the following reactions are the equilibrium constants really unitless quantities? (a) 2 H2 + O2 = 2 H2O (b) 2 NO = N2 + O2 (c) COCl2 = CO + Cl2 (d) CO + H2O = CO2 + H2 (Just give the letter(s) of your choice(s), e.g., ad).

Hint... Two of the statements are correct. There is another reaction for the said condition. Read the question carefully. Give all reactions for the said condition.

Answer bd

Example 1

For the gas phase reaction H2(g) + I2(g) = 2 HI(g) Kc = 50.3 at 731 K. Equal amounts (0.100 M each) is introduced to a container, and then the temperature is raised to 731 K. Is the system at equilibrium? If not, what direction is the reaction? Solution When equal amounts are present,
[HI]2 (0.1)2 Qc = ---------- = -------- = 1 < Kc (50.3) [H2] [I2] (0.1)2

There is a tendency to increase [HI] to reach equilibrium at 731 K.

Example 2

For the gas phase reaction H2(g) + I2(g) = 2 HI(g) Kc = 50.3 at 731 K. Equal amounts (0.100 M each) is introduced to a container, and then the temperature is raised to 731 K. Calculate the concentration of each when the system is at equilibrium.
Solution

For convenience, we write down the reaction equation and put the concentration of the species below the formula. Since the [HI] concentration will increase, we assume x M of H2 or I2 to react to give 2x M of HI.
H2(g) + I2(g) = 2 HI(g) 0.100 0.100 0.100 -x -x 2x 0.1-x 0.1-x 0.1+2x initial concentration amounts change equilibrium concentration

To simplify notation, we ignore the number of significant figure in the formulations. By definition of equilibrium constant, we have
[HI]2 (0.1+2x)2 Kc = ---------- = -------------- = 50.3

[H2] [I2]

(0.1-x)(0.1-x)

Expanding the above equation gives, 46.3 x2 - 10.43x + 0.493 = 0 Please expand the equation to see if you get the same result. Many students have difficulty in deriving or simplifying this equation. Solution of the quadratic equation gives x = 0.067 and x' = 0.158. When x' = 0.158, 0.1 - 0.158 = -0.058. Since concentration should not be a negative value, this solution does not agree with reality. The only acceptable solution is x = 0.067, and thus we have: [H2] = [I2] = 0.100 - 0.067 = 0.033 M [HI] = 2x = 0.100 + 0.134 = 0.234 M It is always a good idea to check the validity of the answer. We use the result to calculate the equilibrium constant. 0.2342 / 0.0332 = 50.3 = Kc. It is helpful to review beginning of this page on the problem solving strategy.
Example 3

At 1100 K, Kc = 4.20e-6 for the gas phase reaction, 2 H2S(g) = 2 H2(g) + S2(g) What concentration of S2 can be expected when 0.200 mole of H2S comes to equilibrium at 1100 K in an otherwise empty 1.00-L vessel?
Solution

We write the equation and place quantities at the initial condition and at various stages below the formula. We assume x mol of S2 is formed, and this leads to the formation of 2x moles of H2. Since -2x moles of H2S is required, the equilibrium concentration of H2S is 0.200 - 2x. Thus, we have
2 H2S(g) = 2 H2(g) + S2(g) 0.200 0 0 initial condition -2x 2x x assume x mole of S2 is formed 0.200-2x 2x x equilibrium concentration

The definition of Kc leads to the equation,

[H2]2 [S2] (2x)2 (x) Kc = ----------- = ------------ = 4.20e-6 [H2S]2 (0.200-2x)2

This is a cubic equation, and there is no general method to solve this type of equations. Fortunately, since the equilibrium constant is very small, we expect x to be a small value. Thus, 0.200 - 2x is almost 0.200. With this approximation, we have a simpler equation to solve: 4 x3 = (0.200)2 * 4.20e-6 = 1.68e-7 3 x = 1.68e-7 / 4 = 4.2e-8 x = (4.2e-8)1/3 = 3.5e-3 = [S2] [H2] = 2 x = 7.0e-3 Discussion: Is the approximation justified? We can calculate the equilibrium constant from the equilibrium concentrations. 4 (0.0035)3 / (0.200-0.007)2 = 4.6e-6 The error in Kc = (4.6-4.2)e-6/4.2e-6 = 4.8%. This is within 5 % criterion, but we are approaching the limit for using approximation. In the approximation, we used 0.200 M instead of 0.193 M as [H2S]. In this example, you have learned the approximation technique. Confidence Building Questions

A 1.00-L container contains 1.00 M of phosgene, which decomposes according to the reaction, COCl2(g) = CO(g) + Cl2(g). At equilibrium, the concentration of Cl2 is 0.028 M. What is the concentration of CO? Hint 0.028 From the equation, [CO] = [Cl2]. Discussion... What is the equilibrium concentration of phosgene?

A 1.00-L container contains 1.00 M of phosgene, which decomposes according to the reaction, COCl2(g) = CO(g) + Cl2(g). At equilibrium, the concentration of Cl2 is 0.028 M. What is the equilibrium constant? Hint 8.0e-4 Kc = (0.028)2/(1-0.028) = ? From the same condition, we can calculate several quantities.

A 2.00-L container contains 1.00 mole each of H2 and I2 gases. When the system reached equilibrium, the concentration of I2 is 0.11. The equilibrium equation is H2(g) + I2(g) = 2 HI(g) What is the concentration of HI? Hint 0.78 M The initial concentration of H2 and I2 is 0.50 M. [HI] = 2*(0.50-0.11) M Discussion... Can the equilibrium constant be calculated?

A 2.00-L container contains 1.00 mole each of H2 and I2 gases. When the system reached equilibrium, the concentration of I2 is 0.11. The equilibrium equation is H2(g) + I2(g) = 2 HI(g) What is the equilibrium constant? Hint 50.3 M At equilibrium, the concentrations are [H2] = [I2] = 0.11, and [HI] = 2*(0.50-0.11) = ? Use these values to calculate Kc.

A 1.00-L container contains 1.00 mole each of H2 and I2 gases. The equilibrium constant Kc = 50 for the equilibrium H2(g) + I2(g) = 2 HI(g).

What is the concentration of H2? Hint 0.22 M

H2(g) + I2(g) = 2 HI(g). 1.0-x 1.0-x 2x

Solve the equation, (2x)2/(1.0-x)2 = 50. A easy way to solve the equation is to take square roots on both sides of the equation as a first step. Discussion... What is [H2] if the container has a volume of 2.0 L?