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GENERAL CHEMISTRY II
- TUTORIAL CLASS FOR MIDTERM EXAM -
Contents
1. Stoichiometry
2. The thermodynamics of chemical reactions
3. The kinetics of chemical reactions
Contents
1. Stoichiometry
2. The thermodynamics of chemical reactions
3. The kinetics of chemical reactions
1.1. Stoichiometry calculation
Stoichiometric calculations are used to determined the relations between the amount of
disappeared reagents and products based on the stoichiometric coefficients of the reaction
equation, which are expressed through molar interpretation : calculate amount of mole.
aA + bB → cC + dD (a, b, c, d > 0)
Stoichiometric mixture: contained reagents are in needed ratio for complete reactions.
Non-stoichiometric mixture: the reagent in excess remains after the reaction while the
limiting reagent is completely consumed (in the case of a complete reaction).
Incomplete reactions: the term yield is used: ratio of the amount of mole reaction product
formed to the amount of mole that theoretically could have been formed, multiplied by
100%.
Example 1: 20 ml of a 0.40 molar solution of Fe(III) ions is diluted to 100ml. 10 ml
of the diluted solution is mixed with 10 ml of a solution that contains 0.60 mmol
Sn(II) ions. Afterwards this mixture is diluted to 50 ml. Calculate the
concentrations of all ions in the mixture.

Just a reminder
1.2. Gas law
For ideal gas

pV = nRT
● p: pressure (Pa/atm) (1 atm = 101325 Pa)
● V: volume (L)
● n: amount of gas mole (mol)
● T: temperature (K)
● R = 8.314 J K-1mol-1 = 0.082 L atm K-1mol-1 (gas constant)

*In approximation, this law also can be used for real gases.
1.3. Dalton’s law of partial pressures
Example 2: A piece of potassium reacts with water. The gas formed is trapped
in a gas burette. The gas volume increases with 36.5 mL. The temperature is
20°C, the pressure is 1,000 atm, and the vapor pressure of water at 20°C is
0.023 atm.

a) Calculate how many gram potassium has reacted.

b) The gas mixture in the setup (gas mixture + excess air) with an electric
discharge is brought to reaction, calculate the decrease of the gas volume,
when the temperature is back to 20°C while pressure stays at 1.000 atm.
Contents
1. Stoichiometry
2. The thermodynamics of chemical reactions
3. The kinetics of chemical reactions
 2.1. Introduction
Sign convention
Thermodynamic systems

Energy is exchanged as work (= structured

energy) and/or heat (= chaotic energy)
2.1. Introduction
Work (W) Heat (Q)

Relation through specific heat capacity (the

amount of heat needed to change the
temperature of 1 g of a substance by 1 K)
Q = Cmasse.m.∆T

Relation through molar heat capacity (the

amount of heat needed to change the
temperature of 1 mol of a substance by 1 K)
Q = Cmolar.n.∆T

*Heat capacity is different in the case of

*(-) sign for making the work become constant pressure and constant volume.
positive as the work is done on the
system
43.06kJ

W = −1140kJ

−354.55J
Exercise:
There are 2 cups (A) and (B) containing 200 mL of HCl 0,8M, respectively. Cup
(A) is added with 200 mL of NaOH 1 mM and cup (B) is added with 400 mL of
NaOH 0.5 mM. Supposing the effects of the surrounding environment is
negligible, what can we expect about the highest temperature of each cup,
knowing that they have the same heat capacity.

(1) The highest temperature of cup (A) is higher than that of club (B)
(2) The highest temperature of cup (B) is higher than that of club (B)
(3) The highest temperature of cup (A) is equal to that of club (B)
(4) We can not expect to guess this without experimental measurements.
2.2. First law of thermodynamics

Internal energy ( ) is the sum of the potential and kinetic energies of all
molecules, atoms and ions in the system.

First law of thermodynamics

dU = dW + dQ

=> The total energy remains constant, although it may be converted from one form to
another (law of energy conservation)

Consequences:

● In an isolated system ΔU = 0
● At constant volume, ΔU = ∆Q (because dW = PdV and ∆V = 0)
2.3. Enthalpy
The enthalpy H is the sum of the internal energy U and the term pV (work).
H = U + pV and ΔH = ΔU + pΔV
At constant pressure: ΔH = ∆Q - pex. ΔV + pΔV = ∆Q (|pex| = |p|)
=> ΔH = heat exchanged at constant pressure
(We also apply this when the question ask us to calculate ΔH for a reaction at a certain
temperature)
For reaction contained gases: ΔH = ΔU + ΔnRT (Δn is the difference in mole of gas
between after reaction and before reaction)
Enthalpy is the state function => Reversing a reaction or a process changes the sign of ΔH
A → B (1) and B → A (2) so we have:
The standard enthalpy of formation of an element ( ) in its standard state is zero.
2.3. Enthalpy

- Standard enthalpy change ΔH° is the enthalpy change of the transformation of substances
at their standard state (gas: p = 1 atm; solid/liquid : most stable state, p = 1 atm. ; dissolved
substance: concentration 1 M and T = 298 K)

*In most of the cases, we can assume that influence of T on ΔH° is negligible

=> Reaction enthalpy (ΔHreaction)?

 2.4. Hess’s law

The enthalpy change of a global process is the sum of the enthalpy changes of the different
steps.

Hess cycle

=> ΔH°reaction = ΣnΔH°f (reaction products) - ΣnΔH°f (reagents)

Hess diagram
2.5. Second law of thermodynamics and Entropy

Entropy S is the parameter that measures the disorder of matter and energy, unit J/K.

Second law of thermodynamics state that the driving force of a spontaneous process is
towards a more chaotic state => Total ΔS during spontaneous process is always positive

Consequences:

● ΔS (isolated system) > 0

● ΔS (total) = ΔS (system) + ΔS (environment) > 0
● S(gas) > S(liquid) > S(solid)

Entropy is a state function:

● ΔS°reaction = ΣnS°(reaction products) – ΣnΔS°(reagents)

● Hess law can be applied for entropy
● Reversing a reaction or a process changes the sign of ΔS
Derivation of second law

Assume that P and T are constant

For irreversible transformation: ΔS (total) = ΔS (system) + ΔS (environment) > 0

For reversible transformation: ΔS (total) = ΔS (environment) = ΔQ/T = dH/T

=> ΔS (total) = ΔS (system) + ΔH (environment)/T

=> ΔS (total) = ΔS (system) - ΔH (system)/T

ΔS (total) > 0 or ΔS (system) - ΔH (system)/T > 0

2.6. Gibbs Free energy

The (Gibbs) free energy is the difference between the enthalpy and the term TΔS:

G = H - T.S and ΔG = ΔH - TΔS

We have ΔS - ΔH/T > 0 or TΔS - ΔH > 0 for spontaneous irreversible reactions (previous
derivation of second law)

=> ΔG < 0 (exergonic) for spontaneous reaction, and ΔG > 0 (endergonic) for nonspontaneous
reaction.

- Free energy is a state function

- Free energy depends on temperature

ΔGreaction = ΔHreaction - TΔSreaction

2.6. Gibbs Free energy

ΔG = ΔG0 + RT ln Q

● ΔG: Change in Gibbs free energy

● ΔG0: Change in standard Gibbs free energy
● R: Ideal gas constant (= 8.314 J/mol)
● T: Temperature (in K)
● Q: Reaction quotient (= [C][D]/[A][B])

At equilibrium: Q = K (equilibrium constant)

ΔG = ΔG0 + RT ln Q = ΔG0 + RT ln K = 0

=> ΔG0 = -RT ln K

 Exercise: Assume that no energy in the form of heat is transferred to
the environment; For water: Heat of fusion = 333 J/g; specific heat
capacities: ice = 2.06 J/gK, liquid water = 4.18 J/gK).
(a) 45.0 g of ice at –10.0 °C is mixed with 90 g of water at 37.0 °C.
Calculate the final temperature of the mixture and tell if it is liquid
or solid.
(b) At –5.0 °C, is liquid water or solid water (ice) more stable? Prove
by calculation.
Exercise:
Contents
1. Stoichiometry
2. The thermodynamics of chemical reactions
3. The kinetics of chemical reactions
 3.1. The reaction rate and the rate law
The rate of a reaction (v from velocity) is
defined as the change of the concentration of The rate law
reaction products (formation) or reagents
(consumption) per time unit. The unit for v is
mol L-1 s-1 .

The global order of the reaction is the sum

of the orders in the reaction equation.

Note: a and b are different from

stoichiometric coefficients of A and B in the
reaction
3.2. Order of reaction

Zero order reaction

Reaction with reagent A

=>

where [A]t is the concentration of A at time t

[A]0 is the initial concentration of A initial

3.2. Order of reaction

First order reaction

Reaction with reagent A => reaction rate = – d[A]/dt = k[A] => - k.dt = d[A]/[A]

Integrating both sides, we have ln[A]t - ln[A]0 = -kt

A pseudo-first order reaction is a reaction of higher order that is carried out in such a way that the
reaction behaves like a first order reaction

Example: H2O2 + 3I- + 2H+ → I3- + 2H2O

Large excess [I-]

=> approximate constant concentration [I-]

=> v = k[H2O2 ][I-] = kpseudo[H2O2]

with kpseudo = k[I-]

3.2. Order of reaction

Second order reaction

Reaction with reagent A and reaction rate = – d[A]/dt = k[A]2 => - k.dt = d[A]/[A]2

Integrating both sides, we have 1/[A]t = kt + 1/[A]0

3.3. Half life

Half life of a reagent is the time needed to reduce the concentration of that reagent to half of
its initial value.

=> Substitute into integrated rate law: t1/2 is the time for [A]t to reach ½[A]0
Exercise: In the reaction A→products:
At t=0 [A]=0.1563M;
After 1.00 minute, [A]=0.1496M;
After 2.00 minutes, [A]=0.1431M;

(a) Calculate the average rate of reaction during the first minute and during
the second minute.
(b) Why are these two rates not equal?
(c) Determine the order of the reaction and calculate the rate constant
3.4. Reaction mechanism

- Many reactions occur in a number of steps, called elementary reactions.

- Law of Mass Action: The rate of a simple (one step) reaction is directly proportional to the
concentration of the reacting substances.

-Intermediates are species that appear in a reaction mechanism but not in the overall balanced
equation

- The step in the reaction mechanism that determines the rate of the global reaction is called the
rate determining step, which is the slowest step in the mechanism.
3.5. Activation energy and energy diagram

- The collision theory: A reaction occurs after a collision between the reagents (X and Y).
Only collisions with sufficient kinetic energy and the right orientation are efficient.

- The activation energy is the minimum amount of energy needed to initiate or start a
chemical reaction.

- Energy diagram:
3.6. Arrhenius equation
=> The dependence of rate constant on temperature

=> At different temperatures, we have the relation of k

3.7. Catalysed reaction

Catalyst is a substance that accelerates the reaction without being used up itself. The
catalyst has an effect on the reaction mechanism that decreases activation energy.

2 types of catalyst:

● Homogeneous catalyst: The catalyst

is in the same phase as the reagents.
● Heterogeneous catalyst: The catalyst
is in another phase as the reagents.
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