Chemical Equilibrium

15.1 – 15.2 Rate of a chemical reaction (reaction rate)

Reaction Rate ● the measure of how ________ the reaction proceeds
● the rate that reactants turn into products per unit of time
● compare fast rate vs slow rate
● rate = -∆[reactants]/∆time
● units: mol/L•s

Collision Theory
Particles must:
● collide with proper ___________
● ____________ energy
● activation energy
Factors Affecting the Rate of the Reaction
1. particle size (solid) -
● small particles versus large particles
2. concentration -
● increased concentration
● decreased concentration
3. temperature -
● increase temperature
● decrease temperature
4. pressure (gas only) -
● increase pressure
● decrease pressure
15.12 Catalyst
catalyst
● _________ up the reaction
● does not get used up (consumed temporarily and reformed)
● lowers the activation energy (__________ pathway)

Ex: enzymes
● biological catalyst
● lock-n-key
Rate Laws
A -> B
In this chemical reaction,
The rate of reactants consumed (-) per unit of time is
● rate = - ∆[A] = - [A]2 – [A]1 =
(M) ← units
∆t t 2 – t1 (s)
● units: mol/L • s

The rate _____ for this reactions is

rate = k[A]x
● k = the rate constant
● x = order of reactant A = order of the reaction, too
● can not be determined from a balanced equation
● can only be determined from __________ evidence

Initial rate method

● used to determine the ______ of each reactant
A + B -> C ● only based on initial concentration of ________

← add exponents to find the order of the reaction = n+m

Practice Problems
1) Write the generic rate law for the following reaction.
A + 2 B -> 2 C

2) What is the order of each reactant and the overall order

of the reaction?
rate = k[A]2[B]
Initial Rates Method
● Studies the effect of a change in reactant
concentrations on the rate of the reaction in
different trials

3) From the data in the following table, write the

rate law for the reaction. Calculate the rate
constant. A -> B

Initial Concentration of A Initial Rate

(mol/L) (mol/L•s)
Trial 1 0.050 0.00030
Trial 2 0.10 0.0012
Trial 3 0.20 0.0048
Practice Problems
4) For the reaction C + D -> E, determine the rate law and
calculate the rate constant for the following data.

Trial 1 Initial [C] Initial [D] rate (mol/L•min)

1 0.010 0.040 6.00 x 10-3
2 0.020 0.040 1.20 x 10-2
3 0.010 0.080 2.40 x 10-2
Practice Problem
5) Determine the rate law and calculate the rate constant for
the following data: A + 2 B -> 2 C

Trial Initial [A] Initial [B] Rate of formation of C (mol/L•s)

1 1.00 0.25 0.26
2 1.00 0.50 0.52
3 1.00 1.00 1.04
4 2.00 1.00 4.16
Practice Problem
6) The reaction of iodide ion with hypochlorite ion, OCl-,
follows the equation: OCl- + I- -> OI- + Cl-

It is a rapid reaction that gives the following rate data

Trial Initial [OCl-] Initial [I-] Rate of Formation of Cl-

(mol/L•s)
1 1.7 x 10-3 1.7 x 10-3 1.75 x 104
2 3.4 x 10-3 1.7 x 10-3 3.50 x 104
3 1.7 x 10-3 3.4 x 10-3 3.50 x 104

What is the rate law for the reaction? Determine the rate
constant.
Equilibrium, Equilibrium Constant
Equilibrium
● forward rate = reverse rate
● reactant and product are constant but not equal
A+B⇄C+D
Equilibrium constant (Keq, Kc) ← big K
● RATIO of product equilibrium concentrations to
reactant equilibrium concentrations raised to the
power of their coefficients
aA + bB <-> cC + dD
Keq = [C]c [D]d [products]eq
[A]a [B]b [reactants]eq

Value of K
● K > 1; products are favored
● K < 1; reactants are favored
Practice Problem
7) Write the equilibrium expression for the following
reactions.
a) 3H2(g) + N2(g) <--> 2NH3(g)

b) PCl5(g) <--> PCl3(g) + Cl2(g)

Practice Problem
8) H2(g) + I2(s) <-> 2HI(g) K = 710
What is favored at equilibrium, products or reactants?
(Hint: look at the K value)
15.5 Heterogeneous Equilibrium
● solids and liquid are not part of the equilibrium
expression
● They are considered pure substances,
not solutions so there is no concentration

Practice Problem
9) Write the equilibrium expression for the following
reaction.
4 HCl(g) + O2(g) <-> 2 H2O(l) + 2 Cl2(g)
15.6 Calculating Equilibrium Constants
● Use with substitution of concentration values to solve
for K
● No units

Example:
N2O4(g) <--> 2NO2(g)
10) A 2.00L of a gas mixture at 15oC at equilibrium contains
0.035 mol N2O4 and 0.45 mol NO2. Write the equilibrium
expression and calculate the equilibrium constant.
Calculate the equilibrium constant if the reaction is reversed.
Solving for equilibrium concentration using K
● Create an ICE Table (only with concentrations)
● Use substitution of K value and K expression to solve
for Equilibrium concentrations
● Must have molarity unit (M) or (mol/L)
● If no concentration is given for a substance, assume
the initial concentration is zero.
● There are no zero-value equilibrium concentrations

Example:
11) Calculate the equilibrium concentration of HI, if the Keq
=
25, the equilibrium concentrations of H2 and I2 are 0.25 M
and1.35 M respectively.

H2(g) + I2(g) <--> 2HI(g)

Practice Problem
N2O4(g) <-> 2 NO2(g)
12) A 0.125 mol sample of dinitrogen tetroxide is introduced
into a 1.00 L container and allowed to decompose at a given
temperature. When equilibrium is reached, the concentration
of the dinitrogen tetroxide is 0.0750 mol/L. What is the value
of Keq for this reaction?

Ice Table:

Initial
Change
Equilibrium
Practice Problem
PCl5(g) <-> PCl3(g) + Cl2(g)
13) Phosphorus pentachloride decomposes to phosphorus
trichloride and chlorine gas. A 1.10 mol/L sample of PCl5
was placed into a vessel. At equilibrium it was determined
that the concentration of PCl5 was 0.33 mol/L. Calculate
the Keq for this reaction.

Ice Table:

Initial
Change
Equilibrium
Le Chatelier’s Principle
● Le Chatelier’s Principle
● when a chemical system at equilibrium is disturbed, the
system __________ in a direction that __________ the
disturbance
● equilibrium position - when a system is at equilibrium
● 3 stressors that ___________ a system from an equilibrium
position
● concentration change
● volume change
● temperature change

● A system will try to __________ its equilibrium position

Three Stressors
N2(g) + 3H2(g) <--> 2NH3(g)
1. concentration
● increase concentration
● decrease concentration
2. pressure (volume) – only _________
● increase pressure
● decrease volume - favors the side with the least
amount of particles
● decrease pressure
● increase volume - favors the side with the most
amount of particles
3. temperature
● decrease temperature
● favors the side with energy
● increase temperature
● favors the side without energy
Practice Problem
PCl5(g) + heat <--> PCl3(g) + Cl2(g)
14) Predict how the system will react with each of the
following changes.

a) addition of Cl2

b) increase in pressure

c) removal of heat

d) removal of PCl3 as it forms

Practice Problem
2H2(g) + O2(g) <--> 2H2O(g) ∆H = -484 kJ

15) Predict how the system will react with each of the
following changes.

a) H2O is removed as it is generated

b) H2 is added

c) the pressure is decreased

d) the system cooled

e) Addition of Ne gas
Practice Problem
N2O4(g) + 58kJ <--> 2NO2(g)
16) Predict how the system will react with each of the
following changes.

a) addition of heat

b) decrease in pressure

c) addition of NO2

d) removal of N2O4

e) Addition of Ar gas
15.11 The Solubility-Product Constant
● solubility product constant (Ksp) ← just another K
● based on the dissolution equation
ex: MNm (s) → M+(aq) + Nm-(aq)
Solubility = the max concentration of the compound (at equilibrium)

● uses the equilibrium concentrations of ions in a ___________

solution
● a solution where the max amount of solid is dissolved
already
Ksp = [M+][Nm-]
● solids and liquids are ______ part of the equilibrium expression

Values of Ksp
● large Ksp more soluble (a lot of ion product formed)
● small Ksp less soluble (not many ions formed)
15.11 The Solubility-Product Constant
Ex:
Write the dissolution equation and Ksp expression for
aluminum hydroxide (s). The Ksp for Al(OH)3 is 5.0 x 10-33.

17) Solve for solubility of Aluminum hydroxide (solve for x).

Al(OH)3 (s) → Al3+ (aq) + 3 OH- (aq)
Practice Problem
18) Write the dissolution equation and Ksp
expression for each solid below.
a) silver iodide (s)

b) barium carbonate (s)

c) calcium fluoride (s)

Practice Problem
● use Ksp -> solve for solubility (concentration of
compound)

19) What is the concentration of zinc ions and sulfide

ions in a saturated zinc sulfide solution at 25oC
(Ksp = 3.0 x 10-23)?
Practice Problem
20) What is the concentration of the copper ions and
iodide ions in a saturated copper (II) iodide solution at
25oC (Ksp = 1.1 x 10-12)?
Practice Problem
● use solubility -> solve for Ksp
21) What is the Ksp of copper(II) sulfide if the
equilibrium concentrations of Cu2+ and S2- in
saturated solution of CuS are each 3.3 x 10-8 M?
Practice Problem
22) What is the Ksp of lead(II) fluoride if the
concentration of lead(II) fluoride is 2.6 x 10-4 M?
Entropy (S)

Law of disorder
● solid → liquid → gas; increase in entropy
● gas → liquid → solid; decrease in entropy
Entropy (S) The Universe is always increasing in disorder
Ex 1: CaCO3(s) --> CaO(s) + CO2(g)
● reactants (solid phase); products (solid & gas phase)
● more moles on the product side; increases S
AND one of the products is a gas

Ex 2: N2(g) + 3H2(g) --> 2NH3(g)

● reactants (gas phase); products (gas phase)
● less moles on the product side; decreases S

● An increase in S; favors a spontaneous reaction

● A decrease in S; favors a nonspontaneous reaction

**Phases will be a bigger factor than moles

If there are more moles of reactants than products,
BUT the phases of the products are gases, it is
considered an increase in S
Practice
23) Which system has the lower entropy
a) 50mL of liquid water or 50 mL of ice

b) 10 g of NaCl(s) or 10 g of NaCl(aq)

24) Predict the direction of the entropy change in each

reaction
a) NH4OH(s) --> NH3(g) + H2O(l)

b) NH3(g) + HCl(g) --> NH4Cl(s)

Change in Entropy
● ∆So
● The entropy “measure” of one mole of a substance
● Standard states ( o ): 1 atm for each gas, 298 K for
the entire system, 1 M for each solution present

∆SoRXN = Σ Sonp - Σ Sonr

Problems
● Complete + balance the chemical reaction.
● Calculate the entropy for the reaction using the data
sheet on planbook.
25) Calcium metal + water ->
Practice
Practice writing chemical reactions and calculate the
entropy for the following.
26) Combustion of ethane (C2H6) (water is gas)
Change in Enthalpy (this is a review)
Review Enthalpy
● ∆H
● heat content of system when pressure remain constant
● ∆H = - exothermic system
● ∆H = + endothermic system

● ∆Hfo (standard heat of formation)

● amount heat change to form 1 mole of substance from its
elements
● standard states – 1 atm for each gas, 1 M for each solution, 298
K for the entire system
● ∆Horeac = Σ ∆Hfonp – Σ ∆Hfonr
Practice
Practice writing the chemical equation and find the
heat of reaction (ΔHo RXN)of the following.
27) combustion of ethane. (C2H6)
FREE ENERGY
● Gibbs free-energy change (G)
● maximum amount of energy to do useful work
∆G = ∆H-T∆S

Processes in nature are driven towards least enthalpy (a negative

value) and towards greatest entropy.

● ∆G is negative; spontaneous Thermodynamically favorable

● ∆G is positive: nonspontaneous Thermodynamically unfavorable

Problems
28) What signs of enthalpy (+ or -) and entropy (+ or -)
values will always give a negative ∆G, thermodynamically
favorable condition?

29) What signs (+ or -) of enthalpy and entropy values will

always give a positive ∆G, thermodynamically unfavorable
condition?
THERMODYNAMICS
The study of the driving force of reactions

There are two forces that can drive a chemical reaction:

- Enthalpy (ΔH) - heat exchange
- Entropy (ΔS) - the change in disorder

★ Remember that the Universe always increases in entropy.

★ Remember that the release of heat (ΔH = -) favors a

spontaneous reaction because it increases the entropy of
the universe (heats up the surrounding).
Practice
30) Calculate the ∆G for the combustion of ethane.
(∆S = 92.6 J/mol•K; ∆H = -2855.60 kJ/mol – from
previous problems)
Practice
31) For the phase change H2O(s) -> H2O (l)
∆Ho = + 6.03 kJ/mol; ∆So = 22.1 J/k • mol
a) Calculate ∆G at 25.0oC

b) Calculate ∆G at -25.0oC
Practice
32) Calculate ∆Go for the following reaction at 25oC and 1
atm
Cr2O3(s) + 2Al(s) <-> Al2O3(s) + 2Cr(s)

∆Ho(kJ/mol) So(J/K mol)

Cr2O3(s) -1128 81
Al(s) 0 28
Al2O3(s) -1676 51
Cr(s) 0 24