1.

Which of the following will not

change the rate of a reaction?
a.adding a catalyst
Answer: D
b.adding more reactants
c.grinding the reactants
d.maintaining the temperature constant
 2. Enzymes are examples of _______.

a.Biological Catalysts Answer: A

b.Biological elements
c.Chemicals that increase the surface
area of reactants
d.Molecules that increase the
concentration of reactants
3. Which of the following reactions
will delay the decay of fruit?

a.putting it in boiling water

b.cutting it into small pieces Answer: C

c.placing it in the refrigerator

d.not wash it with water before
storage
 4. Which of the following will slow down
a chemical reaction?
a.Increasing the volume that the reactants
Answer: A
occupy
b.Increasing the temperature of the reactants
c.Increasing the concentration of the
reactants
d.Increasing the surface area of the reactants
 5. Why does the rate of a chemical
reaction increase with a rise in the
temperature of the reactants?
a. Heat decreases the surface area of particles
available for collision.
b. Heat makes the molecules react more frequently
by increasing their size
c. Heat increases the concentration of the reactants
by evaporating some of them.
d. Heat makes the particles of the reactants move
more rapidly, which enhances the possibility of
collisions. Answer: D
• Which type of reaction takes in heat from its
surrounding?
• EXOTHERMIC OR ENDOTHERMIC?
SURROUNDINGS

HEAT (q)

E(sys) Decreasing

SYSTEM
E(sys) Increasing
Spontaneous and
Non-spontaneous

spontaneous

Non-spontaneous
 Spontaneous and
Non-spontaneous

Non-spontaneous
spontaneous
 Entropy,
Free Energy
and
Equilibrium
 Spontaneous Processes
• Spontaneous: process that
does occur under a specific set
of conditions
• Nonspontaneous: process that
does not occur under a specific
set of conditions
 Spontaneous Processes
• Often spontaneous processes are
exothermic, but not always….
• Methane gas burns spontaneously and
is exothermic
• Ice melts spontaneously but this is an
endothermic process…
 Enthalpy, Entropy, and
Spontaneous Processes
• State Function: A function or property
whose value depends only on the present
state, or condition, of the system, not on the
path used to arrive at that state.
• Enthalpy Change (ΔH): The heat change
in a reaction or process at constant
pressure; Δ H = Δ E + PΔ V.
• Entropy ( S ): The amount of molecular
randomness in a system.
 Entropy
• Entropy (S): Can be thought of as a
measure of the disorder of a system

• In general, greater disorder means

greater entropy
Disruption of the crystal increases the entropy, but the
hydration process decreases the entropy. For dissolution
of NaCl, the net effect is an entropy increase
Entropy and Temperature
 Third Law of Thermodynamics
• The entropy of a perfect crystalline
substance is zero at the absolute zero ( K=0)

Ssolid < Sliquid < Sgas

 Standard Entropy
• Standard entropy: absolute entropy of a
substance at 1 atm (typically at 25C)

What do you notice about entropy values for elements

and compounds?
Units: J/K·mol
 Trends in Entropy
• Entropy for gas phase is greater than that of
liquid or solid of same substance
– I2 (g) has greater entropy than I2 (s)
• More complex structures have greater
entropy
– C2H6 (g) has greater entropy than CH4 (g)
• Allotropes - more ordered forms have lower
entropy
– Diamond has lower entropy than graphite
Entropy Changes in a System
Qualitative
• Ssolid < Sliquid
Entropy Changes in a System
Qualitative
• Sliquid < Svapor
Entropy Changes in a System
Qualitative
• Spure < Saqueous
Entropy Changes in a System
Qualitative
Slower temp < Shigher temp
Entropy Changes in a System
Qualitative
• Sfewer moles < Smore moles
Entropy Changes in a System
Qualitative
Determine the sign of S for the following
(qualitatively)
1. Liquid nitrogen evaporates
2. Two clear liquids are mixed and a
solid yellow precipitate forms
3. Liquid water is heated from 22.5
C to 55.8 C
 The Second and Third Laws
of Thermodynamics
• System: the reaction
• Surroundings: everything else

• Both undergo changes in entropy during

physical and chemical processes
 Second Law of
Thermodynamics
• Entropy of the universe increases in
a spontaneous process and remains
unchanged in an equilibrium process.

• Equilibrium process: caused to occur by

adding or removing energy from a
system that is at equilibrium
 Second Law of
Thermodynamics
• Mathematically speaking:
Spontaneous process:
Suniverse = Ssystem + Ssurroundings > 0

Equilibrium process:
Suniverse = Ssystem + Ssurroundings = 0
 Entropy Changes in the
System
Entropy can be calculated from the table
of standard values just as enthalpy
change was calculated.

Srxn = nS products  mS reactants

 Standard Entropy
• Calculate the standard entropy change
for the following using the table of
standard values. (first, predict the sign
for S qualitatively)
2NH3(g)  N2(g) + 3H2(g)
 Standard Entropy
2NH3(g)  N2(g) + 3H2(g)

Srxn = nS products  mS reactants

= [(1)(191.5 J/K · mol) + (3)(131.0 J/K · mol)]

- [(2)(193.0 J/K · mol)]
= 584.5 J/K · mol - 386 J/K · mol
Srxn = 198.5 J/K · mol (Entropy increases)
(2 mol gas  4 mol gas)
 Your Turn!
• Calculate the standard entropy change
for the following using the table of
standard values. (first, predict the sign
for S qualitatively)
2H2(g) + O2(g)  2H2O (g)
 Entropy Changes in the
Surroundings
• Change in entropy of surroundings is
directly proportional to the enthalpy of
the system.
Ssurroundings   Hsystem

Notice: exothermic process corresponds

to positive entropy change in
surroundings
 Entropy Changes in the
Surroundings
• Change in entropy of surroundings is
inversely proportional to temperature
Ssurroundings  1 / T

Combining the two expressions:

Hsys
Ssurr 
T
 Entropy Changes
If the entropy change for a system is
known to be 187.5 J/Kmol and the
enthalpy change for a system is known
to be 35.8 kJ/mol, is the reaction
spontaneous?
Spontaneous if: Suniv= Ssys + Ssurr > 0

Hsys
Ssurr 
T
 Entropy Changes
Is the reaction spontaneous?

35,800 J/mol
Ssys   120.0J/K  mol
298 K

Suniv= (-187.5) + 120.0 < 0 so the

reaction is non-spontaneous
Third Law of Thermodynamics
• Entropy of a perfect crystalline
substance is zero at absolute zero.

• Importance of this law: it allows us to

calculate absolute entropies for
substances
 18.4 Gibbs Free Energy
G = H – T S

• The Gibbs free energy, expressed in

terms of enthalpy and entropy, refers
only to the system, yet can be used to
predict spontaneity.
 Gibbs Free Energy
• If G < 0,negative, the forward reaction
is spontaneous.
• If G = 0, the reaction is at equilibrium.
• If G > 0, positive, the forward reaction
is nonspontaneous
Predicting Sign of G
 Predicting Temperature from
Gibbs Equation
• Set G = 0 (equilibrium condition)
0 = H – T S

Rearrange equation to solve for T- watch

for units!
This equation will also be useful to
calculate temperature of a phase
change.
 Example
For a reaction in which H = 125 kJ/mol
and S = 325 J/Kmol, determine the
temperature in Celsius above which the
reaction is spontaneous.
H 125 kJ/mol
T    385 K
S 0.325 kJ/K×mol

385 K  273 = 112C

 Standard Free Energy
Changes
Free energy can be calculated from the
table of standard values just as
enthalpy and entropy changes.

Grxn = nG products  mG reactants

 Standard Free Energy
Changes
Calculate the standard free-energy
change for the following reaction.
2KClO3(s)  2KCl(s) + 3O2(g)
Grxn = nG products  mG reactants
= [2(408.3 kJ/mol) + 3(0)]  [2(289.9
kJ/mol)]
= 816.6  (579.8) = 236.8 kJ/mol
(spont)
 18.6 Thermodynamics in
Living Systems
• Coupled reactions
• Thermodynamically favorable reactions
drives an unfavorable one
• Enzymes facilitate many
nonspontaneous reactions
 Thermodynamics in Living
Systems
• Examples:
C6H12O6 oxidation: G° = 2880 kJ/mol
ADP  ATP G° = 31 kJ/mol
Synthesis of proteins: (first step)
alanine + glycine  alanylglycine
G° = 29 kJ/mol
 Thermodynamics in Living
Systems
• Consider the coupling of two reactions:
ATP + H2O + alanine + glycine  ADP +
H3PO4 + alanylglycine
Overall free energy change:
G° = 31 kJ/mol + 29 kJ/mol = 2 kJ/mol
Protein synthesis is now favored.
ATP-ADP Interconversions
 Key Points
• Spontaneous vs nonspontaneous
• Relate enthalpy, entropy and free
energy
• Entropy
– Predict qualitatively
– Calculate from table of standard values
– Calculate entropy for universe
 Key Points
• Free energy
– Calculate from table of standard values
– Calculate from Gibbs equation
– Calculate non-standard conditions
– Calculate in relationship to equilibrium
constant