CHM 116 Spring 2012

Todays Lecture
Section 17.1, 17.2, 17.3

Next Lecture
Read Sec. 17.3, 17.4, 17.5 In Silberberg

Exam 1, Mon. Feb 6, 6:30 7:30, Hall of Music

Exam I TONIGHT: Feb. 6. 6:30 PM Elliott Hall of Music
Plan to arrive by 6:15 pm. Bring your PU ID, your seat assignment, a simple calculator, and pencils.

Good Luck Tonight!

2

Bromocresol Green Equilibrium System

Indicator - substance whose solution changes color due to changes in pH

H+ + In- HIn
blue-green
Bromocresol green structure is abbreviated HIn.

yellow

HIn

Determination of K
H+ + In HIn

[HIn] K= + [H ][In ]

Determine [HIn] and [In-] using spectrophotometry at 2 s. Determine [H+] using pH meter. pH = -log[H+]

Is K constant when the pH (and concentrations) are varied?

Lab Preparation
Chapter 7 Read the ENTIRE lab
Review Appendices C (Volumetric Measurement) and D (Spectroscopy)

Do the prelab on pp 56-7. (For #1

you must show your work.)

Attend recitation.

Lecture 8: Learning Objectives

See Silverberg, pp. 709 710
Specifically concentrate your efforts on the eighteen (18) items in Master These Skills

Kinetics vs. Equilibrium

Kinetics applies to the speed of a reaction, the concentration of product that appears (or of reactant that disappears) per unit time

Speed: dissociation of an acid in H2O

Strong Acid: virtually all HCl dissociates to ions
HCl H+ + Cl-

Weak Acid: less than 10% dissociates to ions

CH3COOH CH3COO- + H+

Speed of a reaction: both complete in <1 sec

Kinetics vs. Equilibrium

Equilibrium applies to the extent of a reaction, the concentration of product that has appeared after an unlimited time in a closed system, or once no further change in concentration occurs
At equilibrium: rateforward = ratereverse

A system at equilibrium is dynamic on the molecular level; no further net change in concentration is observed because the rate of formation = the rate of disappearance of each reactant and product.

Vocabulary & Convention

Reversible Reaction: A reaction that can proceed in either direction. For the reversible reaction: MgCO3 MgO + CO2 MgCO3 can give MgO and CO2 MgO and CO2 can give MgCO3

MgO + CO2

MgCO3

By convention: Reactants still on left, products on the right

Demo

Reversible Reactions
2 NO2(g) N2O4(g) Brown Colorless
Equilibrium is reached at fixed temp (room temp), in closed system

Forward rxn

Backward rxn

rewarmed

Change in Temp alters equilibrium concentrations

Equilibrium
After the temperature stops changing in the 2 NO2 N2O4 reaction

The amounts of reactants and products stop changing. Equilibrium has been reached. Equilibrium: the condition at which the amount, concentration, and/or pressure of reactants and products in a closed system do not change, no matter how long the wait

Equilibrium
Equilibrium achieved

Product conc. increases and then becomes constant at equilibrium Reactant conc. declines and then becomes constant at equilibrium

What is rateforward when [H2] stops changing? Rate = k[H2][I2] if elementary rxn

Equilibrium
Five important ideas about equilibrium:
1. Both reactants and products are present and the system must be closed 2. Constant conditions (constant T, constant P no delta E, etc.)

3. Amounts of reactants and products stop changing, but the reactions do not stop! 4. Reactants and products continue to interconvert
5. sometimes it takes a very long time to reach equilibrium (ex. Rusting metal)

Quantitative Description of Equilibrium

2 NO2(g) N2O4(g) Brown Colorless

This happens to be an elementary reaction:

Ratefwd = kfwd[NO2]2
At equilibrium:

Raterev = krev[N2O4]
rateforward = ratereverse

kfwd[NO2 = krev[N2O4]

]2

k fwd [N 2O 4 ] = k rev [NO 2 ] 2

= Keq

Keq the equilibrium constant. This is a particular ratio of equilibrium concentrations of products and reactants at a particular temperature.

Implication of the Magnitude of the Equilibrium Constant

small K K<<1

large K K>>1

intermediate K K = ~1

1) Small K
2) Large K

N2 (g) + O2 (g)
2 CO(g) + O2 (g)

2 NO(g)
2 CO2 (g)

K = 1 x 10 -30
K = 2.2 x 1022

3) Intermediate K

2 BrCl(g)

Br2 (g) + Cl2 (g)

K=5

Quantitative Description of Equilibrium

The Reaction Quotient: Q
The reaction quotient, Q, is a ratio of the concentrations and/or pressures of the products and reactants in a reaction mixture that may or may not be at equilibrium. wA+xB [C]y[D]z Qc = [A]w[B]x or, if gases Qp = yC +zD PCy x PDz PAw x PBx

Note: Q is based on the balanced equation

Qc based on concentration Qp based on partial pressure of gas

Quantitative Description of Equilibrium

Special Case: Keq = Q
The reaction quotient, Q, is a ratio of the concentrations and/or pressures of the products and reactants in a reaction mixture that may or may not be at equilibrium. wA+xB [C]y[D]z Qc = [A]w[B]x = Kc when system comes to equilibrium yC +zD

Qp =

PCy x PDz
PAw x PBx

= Kp when system comes to equilibrium

Reaction Quotients
Doccam

Write reaction quotients: Qc for a. Qp for b.

a. Cu2+ + 4 NH3 = Cu(NH3)42+

b.

2 P2(g) + 5 O2(g) = P4O10 (g)

Quantitative Description of Equilibrium

Special Case: Keq = Q
The reaction quotient, Q, is a ratio of the concentrations and/or pressures of the products and reactants in a reaction mixture that may or may not be at equilibrium. wA+xB [C]y[D]z Qc = [A]w[B]x = Kc when system comes to equilibrium yC +zD

Qp =

PCy x PDz
PAw x PBx

= Kp when system comes to equilibrium

K in Terms of Pressure
Doccam

Kp = Kc(RT)n
n = coeff prod coeff react (If the total # of moles of gas do not change, then n = 0 and Kp = Kc)
A consequence of the gas law:

n P = RT V
Partial pressure Concentration (mol/L)

Concentration of a Pure Liquid

What is the concentration of H2O (M.Wt. 18 g/mole) in 18 mL of water (18 g)?

1 mole/0.018 L = 56 M
What is the concentration of H2O (M.Wt. 18 g/mole) in 1,800 mL of water (mass 1,800 g)? 100 mole/1.8 L = 56 M
The concentration of water does not change as the volume of water changes. The concentration of a solid, a liquid, or a solvent does not change even if its volume changes. So leave out of Q & K equations!

The reaction quotient for a heterogeneous system.

solids do not change their concentrations

CaCO3(s) > CaO(s) + CO2 (g) Partial pressure of CO2 is the same in both jars

The reaction quotient for a heterogeneous system.

Because the concentration does not change, we do not include the concentration of solids, pure liquids, or solvents in a reaction quotient. Doccam [solid], [liquid], [solvent] = 1 Write reaction quotients for a. CaCO3(s) b. 2 H2O2(aq) CaO(s) + CO2(g) 2 H2O(l) + O2(g) Qp = Qc =

c. NH3(g) + HCl(g)

NH4Cl(s)

Qp =

Writing the Reaction Quotient for an Overall Reaction

For: N2 (g) + 2 O2 (g) 2 NO2 (g) [NO2]2 Qc (overall) = [N2][O2]2

For the individual steps:

(1) N2 (g) + O2 (g) (2) 2 NO(g) + O2 (g) [NO]2 2 NO(g) Qc1 = [N2] [O2] [NO2]2 2 NO2 (g) Qc2 = [NO]2 [O2] [NO2]2 [N2][O2]2

[NO]2 x [NO2]2 = Qc1 x Qc2 = [N2] [O2] [NO]2 [O2]

Q1 x Q2 x Q3 = Qoverall (Overall Q is product of all Qs)

i.e. For the sum of reactions, the overall Q is the product of Qs

Q and K for an Overall Reaction

For: N2 (g) + 2 O2 (g) Q1 x Q2 x Q3 = Qoverall likewise K1 x K2 x K3 = Koverall If an overall reaction is the sum of two or more reactions, the overall Q (or K) is the product of the individual Q (or K) Keq is independent of mechanism! Can use stoichiometry of equation to calculate Q (or K) 2 NO2 (g) [NO2]2 Qc (overall) = [N2][O2]2

The Form of Q for a Forward and Reverse Reaction

Sulfur dioxide reacts with oxygen to form sulfur trioxide. 2 SO2 (g) + O2 (g) [SO3]2 Qc(fwd) = [SO2]2[O2] This reaction is reversible. What is Q for the reverse reaction? 2 SO3 (g) 2 SO2 (g) + O2 (g) 2 SO3 (g)

[SO2]2[O2] = Qc(rev) = [SO3]2

1
Qc(fwd)

The equilibrium expression for a reaction written in reverse is the reciprocal of that for the original reaction.