MEBERC PhyChem

- study of underlying principles that govern the properties
and behavior of chemical systems.
MatSciPhyChem Engr. SuzzydTE

Statistical Quantum
Thermodynamics
Mechanics Chemistry
Kinetics

 System – portion of the universe chosen for study
 Surroundings – universe less the system
• Isolated System – does not permit the transfer of both matter &
energy
• Open System – allows the transfer of both matter & energy
• Closed System – does not permit the transfer of matter but allows
the transfer of energy

 State – defined by specifying a number of thermodynamic variables
for the system under study
 Temperature (T) = °C, K, R, °F
 Pressure (P) = Pa, psi, atm, mmHg, Torr, bar
 Volume = m3, ft3, L
 Composition = wt.%, x, M, m
• Steady state - there is no accumulation of mass or energy within

the control volume, and the properties at any point within the
system are independent of time.

 Extensive property – for a system that can be divided into parts any
property of the system that is the sum of the property of the parts
• volume, amount of substance, energy, enthalpy, Gibbs function,
Helmholtz function and entropy
 Intensive property – a system property that can have the same value
for each of the parts
• temperature, pressure, density

 Homogeneous phase - If the system has the same composition and
density throughout
 Heterogeneous phase - density and composition may vary
 Equation of state
- mathematical expression used to describe the state of a system
- must contain the minimum number of variables required to define
the state of a system
- only takes into consideration equilibrium states
- provides only the initial and final states of the system

 Cyclic Process - when a system in a given initial state goes through a
number of different changes in state (going through various processes)
and finally returns to its initial values
 Reversible Process - once having taken place, can be reversed, and in

so doing leaves no change in either the system or surroundings
 Irreversible Process - cannot return both the system and the

surroundings to their original conditions. That is, the system and the
surroundings would not return to their original conditions if the
process was reversed
 Boyle’s Law: P1V1= P2V2
 Amonton’s Law: P1/T1= P2/T2
 Charles’ Law: V1/T1= V2/T2
 Ideal Gas Law: PV = nRT
• Avogadro’s number: 1 mole = 6.022 x 1023particles

• Gas constant: R = 0.08206 L·atm/mol·K
= 1.987 cal/mol·K
= 8.314 J/mol·K
• STP conditions: 0°C and 1atm
(for gases) 1g·mole = 22.4L
1lb·mole = 359.05ft3
 total pressure exerted by a mixture of gases is equal to the sum of the
partial pressures (pressure exerted by a gaseous component if it
occupied the container alone)
Ptotal = P1+ P2+ P3+ … + Pi
where:
P1, P2, P3, … , Pi= partial pressures
such that
Pi= xi Ptotal

1. What is the pressure of 1 mole of an ideal gas confined to a 1.0L
container at 0°C?
nRT 1mol 0.082057 L - atm/mol - K 273.15K 
P 
1.0L
P  22.414 atm
V

2. In an industrial process, nitrogen is heated to 500K in a vessel of
constant volume. If it enters the vessel at 100 atm and 300K, what
pressure would it exert at the working temperature if it behaved as a
perfect gas?
3. The mass percentage composition of dry air at sea level is

approximately 75.5% N2, 23.2% O2 and 1.3% Ar. What is the partial
pressure of each component when the total pressure is 1 atm?

 First Law of Thermodynamics
 Second Law of Thermodynamics
 Third Law of Thermodynamics
 Zeroth Law
 When were the laws of thermodynamics first described?
• Natural laws into Standards
• Theory and Suggestions into Scientific Facts
• James Prescott Joule – First Law of Thermodynamics
• Robert Clausius – Second Law of Thermodynamics
• Walther Nernst – Third Law of Thermodynamics
• Ralph Fowler – Zeroth Law of Thermodynamics

Law of Conservation of Energy
 “Energy can neither be created nor destroyed, but rather
transformed from one state to another.”
 “The total amount of energy in the universe is constant.”

Law of Increased Entropy
 “The universe tends toward high entropy.”
 “Molecules move (diffuse) from an area of high concentration
to areas of low concentration.”

Law of Absolute Zero
 “All molecular movement stops at a temperature we call
absolute zero, or 0 Kelvin (-273.15oC or -459.7oF).”
 “As a system approaches absolute zero, all processes cease
and the entropy of the system approaches a minimum value.”

Law of Thermal Equilibrium
 “When two objects are separately in thermodynamic
equilibrium with a third object, they are in equilibrium with
each other.”
 “Objects in thermodynamic equilibrium have the same
temperature.”

Concepts:
1. Work – motion against an opposing force
2. Heat – transfer of energy due to temperature difference
3. Energy – capacity to do work
Internal Energy, U
 Total sum of the kinetic and potential energies of a system
 Units: 1 J = 1 kgm2/s2 = beat of the human heart
1 cal = 4.184 J
= energy required to raise the temperature of 1g
of water by 1C (14.5 C – 15.5 C)
U = q – W
• + q for endothermic rxn
• - q for exothermic rxn
• +W for work done by the system to the surroundings
• -W for work done on the system by the surroundings

 Described as the interaction between a system and its surroundings
 Comes in different forms:

• Mechanical Work = F*d
• Gravitational Work = m*g*h
• Work of expansion = p*V
 Cannot be evaluated without knowledge of path

F WORK OF COMPRESSION:
• work is done on the system
dx • V 2 < V1
GAS,
v1
GAS, • w is negative
v2
WORK OF EXPANSION:
w  force x distance
• work is done by the system
at infinitesi mal dimensions : • V 2 > V1
dw  Fdx • w is positive
but F  PA
where A is the x - sectional FREE EXPANSION:
area of the piston • expansion against zero
so dw  PAdx  PdV opposing force
V • w is zero
w  V 2 PdV
1
 Useful simplifications:
• Constant Volume – Isochoric
• Constant Pressure – Isobaric
• Constant Temperature – Isothermal
• No Heat Flow - Adiabatic

 carried out at constant volume
 Since there is no change in volume, w = 0
U = q

 carried out at constant pressure
 Work may be reported as the product between pressure and the
change in volume (W = pdV)
U = q – pdV
U2 - U1 = q – p (V2-V1)

 carried out at constant temperature
0=q–W; q=W
W =  p dV =  (nRT / V) dV = nRT  dV / V
W = nRT ln (V2 / V1)
W = nRT ln (P1 / P2)

 no heat flow
U = -W
P1V1 = P2V2
T1V1-1 = T2V2-1
T1P1-1 = T2P2-1
 = Cp/Cv
 A form of energy that when transferred into a system produces a rise
in temperature
 Its transfer is irreversible, which can only be from a body of high

temperature to a body of low temperature
q = CT
where C is the heat capacity (quantity of heat needed to raise

temperature a degree higher)

 Amount of heat required to raise temperature by 1°
 It is the measure of responsiveness of the system to the difference in

temperature.
 The ratio of the energy input to temperature increase depends strongly

on the nature or heat absorbing ability of the substance.

 Heat capacity is an extensive property
• Specific Heat Capacity – amount of heat required to increase the

temperature of 1 gram of a substance by 1°
• Molar Heat Capacity – amount of heat required to increase the

temperature of 1 mole of a substance by 1°

 At constant V, all the heat invested for the gas goes into increasing its
temperature
Cv = dU / dT
 At constant P, the same amount of heat is required to raise the

temperature of the gas at the same level. However, an additional energy is
required to expand the gas
Cp = dH / dT

• Relationship between heat capacity at constant volume and heat
capacity at constant pressure:
C p  Cv  R C p  Cv always
 For monoatomic ideal gas:

Cv = 3/2R ; Cp = 5/2R
 For polyatomic ideal gas:
Cv > 3/2R ; Cp > 5/2R

Q  mcT Q = amount of heat needed to raise temp by T
m = mass of the body
c = specific heat capacity
Q  nMcT n= number of moles
M = molecular mass
Q  nCT C = molar heat capacity

4. How much heat is needed to raise the temperature of 725g of lead from
room temperature (298 K) to its melting point (602 K)? cPb=128 J/kg-K
Q  mcT
Q  0.725kg128J/kg - K 602K - 298K 
Q  28.2kJ

5. Ten liters of an ideal gas at 25°C and 10
atmospheric pressure (state a) are expanded
to a final pressure of 1 atm (state c). The
molar heat capacity of the gas at constant
volume, cV is 3/2R and is independent of
temperature. Calculate the work done, the
heat absorbed, and the changes in internal
energy and in enthalpy for the gas if the
process is carried out:
a. isothermally and reversibly
b. adiabatically and reversibly
• An extensive property used to quantify the heat content of the system.
H  U  PV
H  q p
Interpretation: Enthalpy change is equivalent to the heat absorbed or
evolved.
Enthalpy is not Heat!!!
“Enthalpy” is sometimes described as the heat content of a system under
a given pressure, whereas "heat" is defined as thermal energy in transit.

• When heat is evolved, ∆H < 0
• When heat is absorbed, ∆H > 0
• The value of ∆H always refers to quantities in moles.

Enthalpy Calculations:
H = U + pV = U + nRT
At constant pressure, H = nCpT
When Cp is not constant, it can be expressed as: p 2
p 2
2 2
2 1 2 1
2 1

Standard Enthalpy Changes, H
– change in enthalpy for a process in which the reactants and
products are in their standard states
 Enthalpies of Physical Change

Hvap = Evaporation
Hfus = Fusion or Melting Example: Given a reaction 2A + B = 3C + D
Hsub = Sublimation
Htrans = Transition ( to ) Hr = Hproducts – Hreactants
 Enthalpies of Chemical Change Hr = [3HC + HD] – [2HA + HB]
Hr = Reaction
Hc = Combustions
Hf = Formation
6. Calculate the heat of reaction when limestone is calcined to CaO and
CO2 at 298K.
CaCO3  CO2  CaO
∆H f(CO2) = -151.9 kcal/mol ∆H f(CaO) = -94.05 kcal/mol
∆H f(CaCO3) = -288.45 kcal/mol
H rxn
o
 H of ( CO 2 )  H of ( CaO )  H of ( CaCO3 )
H rxn
o
 151.9  94.05  (288.45)
H rxn
o
 42.5kcal / mol
7. Find the enthalpy of the following reaction at 298 K and 1 atmosphere.
MnSiO3( s )  MnO( s )  SiO2 ( quartz )
Given the following heats of formation:

(1) Mn( s )  12 O2  MnO( s )
H  o, f
298 MnO  92kcal
(2) Si( s )  O2 ( g )  SiO2 ( quartz)
H  o, f
298 SiO2  210.2kcal
(3) Mn( s )  Si( s )  32 O2 ( g )  MnSiO3( s )
H  o, f
298 MnSiO3  5.90kcal / mole
 Gibbs describes the entropy of a system as being a measure of its
“mixed-up-ness” at the atomic or molecular level.
 Entropy is an extensive property of the system as it depends on the

mass of the system.
 In addition, entropy is a state function.
 Clausius coined the term "entropy" to refer to the dissipated potential.

Does the entropy increase or decrease for the following reactions?
a. CaCO3(s)  CaO(s) + CO2(g)

b. N2(g) + 3H2(g)  2NH3((g)
c. NH4NO3(s)  NH4+(aq) + NO3-(aq)
d. H2O(g)  H2O(l)

 For a reversible process, the sum of the change in entropy of the
system and of the surroundings is always zero:
S system  S surroundings  0
 For an irreversible process, the sum of the entropy change of the

system and of the surroundings is a positive quantity:
S system  S surroundings  0

 The entropy change accompanying a chemical reaction, generally
evaluated at constant pressure and temperature, is defined as:
S   Sproducts   Sreactants
 The equation above requires that the entropies of all reactants and
products at the desired temperature is known.

General Form:
q
dS 
T
T2 q
S  ST2  ST1  
T1 T
For plain transformation:
H o
S  Tr
TTr
At constant Pressure:
C p dT
dS 
T
At constant Volume:
Cv dT
dS 
T
If Pressure and Volume are not constant:
Cv dT RdV
S   
T V
At constant Temperature:
RdV  V2 
S    R ln  
V  V1 

8. The phase transition of Sn from gray to white occurs reversibly at 13°C
or 286K (below room temperature). Calculate the change of entropy.

9. One mole of ideal gas is expanded isothermally from a volume of 0.35
cc to 22400 cc. Calculate the change in entropy of the gas in cal/mol-K.

10. Calculate the change in entropy when 50 kJ of energy is transferred
reversibly and isothermally as heat to a large block of copper at:
(a) 0°C (b) 70°C
11. A sample consisting of 2 mol of diatomic perfect gas molecules at 250

K is compressed reversibly and adiabatically until its temperature reaches
300 K. Given that Cv = 27.5 J/mol K, calculate q, w, ΔU, ΔH and ΔS.

 Work that may be obtained from the system.
 Total amount of energy available to be converted to work.
 There are two forms:

• Helmholtz Free Energy
• Gibbs Free Energy

 Maximum work that can be obtained from the system.
F  U  TS
 This value is used for constant T and V problems. Mostly used for
chemical reactions/ systems involving pressure changes (such as in
chemical explosives).

12. When 1.00 mol C6H12O6 (glucose) is oxidized to carbon dioxide and
water at 25°C according to the equation
𝐶6 𝐻12 𝑂6 (𝑠) + 6𝑂2 (𝑔) → 6𝐶𝑂2 (𝑔) + 6𝐻2 𝑂(𝑙) ,
calorimetric measurements give ΔU = -2808kJ/mol and ΔS = +182.4J/molK
at 25°C. How much of this energy change can be extracted as:
(a) heat at constant pressure
(b) work

 The Helmholtz Free Energy plus work done by the system when V is
not constant.
G  H  TS
 Used mostly for open systems involving phase transformations (change

in volume).

G  0, reaction is spontaneous
G  0, reaction is in equilibrium
G  0, reaction is non - spontaneous

Consider the chemical reaction:
lL  mM  qQ  rR
the standard free energy change at 25°C is:
G o
298 , reaction   G o
298 , products   G o
298 , reactants
G o
298 , reaction  qG
o
298 ,Q  rG o
298 , R  lG o
298 , L  mG
o
298 , M

 For stable elements, G298  0
0
 Gibbs Free Energy is an extensive property. Similar to enthalpy, ∆G of

different reactions may be manipulated, provided that the data given
are taken at the same conditions.
 Units are in Joules or calories per mole of substance.

13. Given the reaction:
𝐶12 𝐻22 𝑂11 (𝑠) + 12𝑂2 (𝑔) → 12𝐶𝑂2 (𝑔) + 11𝐻2 𝑂(𝑙)
(a) Calculate the standard reaction entropy at 298 K.
(b) Calculate the standard reaction Gibbs energies at 298K.
(c) Using the standard Gibbs energies of formation, calculate the standard
reaction Gibbs energies at 298 K.
Given Values:
𝑪𝟏𝟐 𝑯𝟐𝟐 𝑶𝟏𝟏 (𝒔) 𝑶𝟐 (𝒈) 𝑪𝑶𝟐 (𝒈) 𝑯𝟐 𝑶(𝒍)
∆𝑺𝟎 (J/molK) 360.2 205.14 213.74 69.91
∆𝑮𝟎𝒇 (kJ/mol) -1543 0 -394.36 -237.13
∆𝑯𝟎𝒄 (kJ/mol) -5645
 A combination of two or more components physically combined so as
to form a homogeneous mixture (exhibits the same physical and
chemical properties throughout the mixture)
Components Homogeneous Mixture
Elements Exhibits the same physical and
Compounds chemical properties throughout
the mixture

 In a binary system, components may be classified as solvent and solute.
Solvent
Component present in the greatest amount;
Also host atoms
Solute
Component present in a minor concentration

1. Weight percent (wt/wt) = (mass of solute / mass of solution) * 102
Parts per thousand = (mass of solute / mass of solution) * 103
Parts per million = (mass of solute / mass of solution) * 106
Parts per billion = (mass of solute / mass of solution) * 109
2. Volume percent (v/v) = (volume of solute / volume of solution) * 102
*only if both are liquids
3. Mole Fraction (Xsolute) = (moles of solute / moles of solute + moles of solvent)
Xsolvent = (moles of solvent / moles of solute + moles of solvent)
4. Molality (m) = (moles of solute / kilograms of solvent)
5. Molarity (M) = (moles of solute / liters of solution)

 Solute-Solvent Relation
“Like dissolves like” – Polar solvent dissolves polar solute
 Common-Ion Effect
Describes the decrease in solubility of an ionic compound when a
salt that contains an ion that already exists in the chemical
equilibrium is added to the mixture.

 Temperature
a. Solids
• Decrease in solubility if the reaction is exothermic (by Le Chatelier Principle)
• Increase in solubility if the reaction is endothermic
b. Liquids
• No defined trends (less likely to encounter L-L solvent-solute mixture)
c. Gases
• Increase in temperature decreases solubility of gases due to increase of kinetic
energy of gases which eventually cause them to escape to the gas phase

 Agitation
a. Solids and liquids

• Increase in “rate” of solubility due to increased frequency of contact of the
surface of the solute and fresh solvent.
b. Gases
• Decreased in solubility if vortex is formed since it is a region of low pressure
which causes the gas to flow out from the liquid phase

14. How many gallons of 3% acid solution must be mixed with
60 gallons of 10% acid solution to obtain an acid solution that
is 8%?
15. How many liters of 20% alcohol solution should be added

to 40 liters of a 50% alcohol solution to make a 30% solution?

 properties of a liquid that may be altered by the presence of a solute.
 Colligative means "depending on the collection" because the
magnitude of the change is due to the number of particles in the
solution and not their chemical identity.
1. Vapor Pressure Lowering ∆P = P°xi (Raoult’s Law)

where: ∆P = extent of vapor pressure lowering
P° = vapor pressure of pure solvent
xi = mole fraction of the solvent in the solution

2. Boiling Point Elevation ∆tb = kbm

where: ∆tb = tbsolution – tbsolvent
kb = ebullioscopic constant
m = molality

3. Freezing Point Depression ∆tf = kfm

where: ∆tf = tfsolvent – tfsolution
kf = cryoscopic constant
m = molality

4. Osmotic Pressure, π π V = nRT

– minimum pressure required to prevent osmosis
where: V = volume of solution
n = moles of solute
T = absolute temperature

16. The vapor pressure of 2-propanol is 50 kPa at 338.8°C, but
it fell to 49.62 kPa when 8.69 g of an involatile organic
compound was dissolved in 250 g of 2-propanol. Calculate
the molar mass of the compound.

 Established after a certain time such that
reactants and products coexist at equilibrium.
Rateforward = Ratereverse
Equilibrium Constant, K – expressed in terms of concentration:

Gases = Partial Pressure, pi
Liquid solutions = Molarity, M
Solids = Activity, ai

 For a reaction: aA + bB ↔ cC + dD
 The equilibrium constant, K, is the ratio of the equilibrium concentrations of

products over the equilibrium concentrations of reactants each raised to the
power of their stoichiometric coefficients.

Characteristics:
1) Equilibrium can be approached from either direction
2) Does not depend on the initial concentrations
3) K does depend on temperature
Magnitude of K Direction of Reactant and Product
Equilibrium Concentration
If K >> 1 Equilibrium lies to the Reaction mixture contains
right mostly products
If K <<1 Equilibrium lies to the Reaction mixture contains
left mostly reactants
If 0.10 < K < 10 Reaction is near Mixture contains appreciable
equilibrium amounts of both reactants
and products
 Heterogeneous equilibria: reactants and products are present in
more than one phase
Example: Write the K expression for the following:

1) CaCO3(s) ↔ CaO(s) + CO2(g)
2) 3Cu(s) + 2NO3-(aq) + 8H+(aq) ↔ 3Cu2+(aq) + 2NO(g) +4H2O(l)

WHAT DOES THE EQUILIBRIUM CONSTANT TELL US?
Predicting the Direction of Reaction

The reaction quotient, Q, is the resulting value when we substitute reactant
and product concentrations into the equilibrium expression.
1. If Q > K, the reaction will go to the left.

• The ratio of products over reactants is too large & the reaction will move
toward equilibrium by forming more reactants
2. If Q < K, the reaction will go to the right.
• The ratio of products over reactants is too small & the reaction will move
toward equilibrium by forming more products
3. If Q = K, the reaction mixture is already at equilibrium, so no shift occurs.
Le Chatelier’s Principle
• If a dynamic equilibrium is disturbed by changing the conditions, the

position of equilibrium moves to counteract the change.
• If a system at equilibrium is disturbed by an external stress, the system

adjusts to partially offset the stress as the system attains a new
equilibrium position.

• dictates changes in equilibrium direction due to the following factors

that affect the position of equilibrium:
 Concentration
 Volume and Pressure
 Temperature
 Effect of a catalyst

1. Changes in Concentration
⇒ Adding a reactant or product, the equilibria shifts away from the increase in
order to consume part of the added substance.
⇒ Removing a reactant or product, the equilibria shifts toward the decrease to
replace part of the removed species.
Example: For H2 + I2 ↔ 2HI, where does the equilibria shift if we:

a) add H2?
b) remove I2?

2. Changes in Volume and Pressure

⇒ If P increases (V decreases), the system shifts to the side with a smaller
number of gas molecules (this effectively reestablishes equilibrium by
decreasing the pressure).
⇒ If P decreases (V increases), the system shifts to the side with a greater
number of gas molecules.
Example: For N2(g) + 3H2(g) ↔ 2NH3(g), does the equilibrium shift left or right if the
pressure is increased?

3. Changes in Temperature
Heat can be considered a reactant in an endothermic reaction and a product
in an exothermic reaction:
Endothermic (∆H > 0) Reactant + Heat ↔ Products
Exothermic (∆H < 0) Reactant ↔ Products + Heat
 K is larger when the reaction shifts right. This occurs if T is increased for an
Endothermic Reaction or T is decreased for an Exothermic reaction.
 K is smaller when the reaction shifts left. This occurs if T is decreased for an
Endothermic Reaction or T is increased for an Exothermic reaction.
3. Changes in Temperature
Example: If the temperature is decreased for the reaction:

2CO2 ↔ 2CO + O2, ∆H = 566 kJ
a) Will the equilibrium shift left or right?

b) Does K become larger or smaller?

4. Effect of a Catalyst
⇒ Catalysts lower the activation energy for the reaction, so a catalyst
decreases the amount of time taken to reach equilibrium for both the forward
and reverse reactions.
⇒ The catalyst does not affect the equilibrium concentrations of reactants and
products in the equilibrium mixture; thus, K value does not change.

General Equation:
∆G = ∆G° + RTlnK (for non-standard conditions)
At equilibrium, ∆G = 0. Such that: ∆G° = -RTlnK

17. The equilibrium pressure of H2 over solid uranium and uranium
hydride, UH3, at 500 K is 139 Pa. Calculate the standard Gibbs energy of
formation of UH3(s) at 500 K.

18. Carbon forms two gaseous oxides, CO and CO2, according to:
At standard state, pCO = pCO2 = 1, thereby making P = 2 atm. If it is

required to decrease the pressure of the system from 2 atm to 1 atm,
a. determine the temperature of the system such that pCO = pCO2= 0.50
atm.
b. determine the equilibrium pO2

 Rate at which the concentration of a reactant decreases or the
rate at which concentration of a product increases
eg. Given the reaction: A  B,

 Rate of change of the concentration of a reactant or product
divided by its stoichiometric coefficient
eg. Given the reaction: N2 + 3H2 = 2NH3,

19. How is the rate at which ozone disappears related to the rate at which
oxygen appears in the reaction:
2O3(g)  3O2(g)
20. If the rate at which O2 appears is 6.0×10–5 M/s at a particular instant, at

what rate is O3 disappearing at this same time?

 An equation that links the reaction rate with concentrations or
pressures of reactants and constant parameters
For the reaction: aA + bB = P

The rate law reads : rate = k[A]x[B]y
• [A] is the concentration of species A,
• x is the order with respect to species A.
• [B] is the concentration of species B,
• y is the order with respect to species B, and k is the rate constant.
• n, is the reaction order for the whole chemical reaction. This can be found by adding the
reaction orders with respect to the reactants. In this case, n = x + y.

Given the reaction: A  products
If a reaction is zero order in a

particular reactant, changing
its concentration will have no
effect on the rate as long as
the reactant is present.

The reaction is first order in a

reactant if the concentration of a
particular component is doubled,
the rate doubles and triples
when the concentration is
tripled.

If the rate is second order with respect
to a particular component, doubling its
concentration increases the rate by a
factor of 22= 4.
Tripling its concentration increases the

rate by a factor of 32= 9
…and so forth.
 Time required to decrease the concentration of the reactants to half
its initial value
Zero-order:
First-order:
Second-order:

 Describes the relationship between rate of reaction and temperature
using thermodynamic functions
or
where k = rate of reaction

A = constant (frequency factor)
Ea = activation energy
R = gas constant
T = temperature in K

2NO (g) + O2 (g) 2NO2 (g)
21. A rate expression for the reaction above is:
-d[O2]/dt = k[NO]2[O2]
ΔHf (kcal/mol) ΔS (cal/mol-K) ΔGf (kcal/mol)
NO (g) 21.6 50.34 20.72
O2 (g) 0 49.00 0
NO2 (g) 8.09 57.47 12.39
(a) For the reaction above, find the rate constant at 25°C if the initial rate is 28 mol/L-s
when the concentration of nitric oxide is 0.20 mol/L and the concentration of
oxygen is 0.10 mol/L.
(b) Calculate the equilibrium constant for the reaction at 25°C.
– branch of science that examines the phenomena resulting from
combined chemical and electrical effects
– study of systems in which electricity plays a role in the changes that
occur during a reaction
Redox reaction
– a chemical reaction wherein a transfer of electrons takes place
• Reduction = gain of electrons
(The substance reduced is the oxidizing agent)
• Oxidation = loss of electrons
(The substance oxidized is the reducing agent)
Two types of electrochemical processes:
1. Electrolytic processes
– Reactions in which chemical changes
occur on the passage of an electrical
current
2. Galvanic or Voltaic processes
– Chemical reactions that result in the
production of electricity
– Galvanic Cell = A device in which chemical
energy is changed to electrical energy
Oxidation occurs at the anode
Reduction occurs at the cathode

Standard Cell Notation
1. Anode components are listed on the left
2. Cathode components are listed on the right
3. Double line represents salt bridge or porous disk
Anode electrode | Anode electrolyte || Cathode electrolyte | Cathode electrode

Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
– driving force on the electrons
– magnitude of the ability of a galvanic cell to push electrons through the
external circuit
Voltage (V)
• defined as the amount of energy (J) that can be delivered per
unit of charge (C) as the current moves through the circuit
• 1 V = 1 J/C

– maximum potential that a galvanic cell can generate
– varies with the amount of current flowing through the circuit
– depends on the following factors:
i. Composition of electrodes
ii. Concentrations of the ions in the half cells
iii. Temperature

 Standard Cell potential
– Potential of the cell in which all of the ion concentrations
are 1.00 M, the temperature is 25°C, and any gases that are
involved in the cell reaction are at a pressure of 1 atm

 Reduction potential
– Magnitude of the half cell’s tendency to acquire electrons
and proceed as a reduction reaction
– Standard Reduction Potential (SRP) = done under
standard conditions

 Standard hydrogen electrode
– a reference electrode that is used because the standard
reduction potential has arbitrarily chosen to be 0 V

“For a set of 2 competing reactions, the reaction with the lower
standard reduction potential gets oxidized while the other proceeds as
a reduction”
 SRP = Oxidized
 SRP = Reduced
Example: Given the following values, Zn is oxidized and Cu is reduced.

Zn2+ + 2e = Zn E°red = -0.76 V
Cu2+ + 2e = Cu E°red = 0.34 V
The electrode potential for a reaction is derived directly from the free energy
change for that reaction:
∆G° = -nFE°cell
where: n = # of moles of electrons transferred
F = Faraday’s constant (96485 C / mole electrons)
E°cell = standard cell potential
Since, ΔG = ΔG° + RT ln Q
Hence,
Nernst Equation

 Explains the relationship between the quantity of current (charge)
passed through a system, and the quantity of (electro) chemical
change that occurs due to the passage of the current
“The mass of an element liberated on an electrode during electrolysis is

directly proportional to the quantity of electricity which passes through
the solution of an electrolyte.”

Mathematically,
𝑴𝑾 𝒙 𝑰 𝒙 𝒕
𝒎=
𝒏𝒙𝑭
where:
m = mass of substance deposited/lost
MW = molecular weight of the substance
I = current passed (A)
t = time for which the current is passed (s)
n = number of electrons transferred
F = Faraday’s constant (96485 C / mole electrons)

22. Write the cell reaction and electrode half-reactions and calculate the standard emf
of the cell:
Pt | Cl2(g) | HCl (aq) || K2CrO4(aq) | Ag2CrO4(s) | Ag
23. Devise the cell with the reaction below and calculate the standard emf:
2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g)
24. Calculate the equilibrium constants of the following reactions at 25°C from
standard potential data:
Sn (s) + CuSO4 (aq) Cu (s) + SnSO4 (aq)
25. How long must a current of 5.00 A be applied to a solution of Ag + to produce 9.7 g
of silver metal?

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- study of underlying principles that govern the properties

and behavior of chemical systems.

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

• Steady state - there is no accumulation of mass or energy within

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

 Reversible Process - once having taken place, can be reversed, and in

 Irreversible Process - cannot return both the system and the

• Avogadro’s number: 1 mole = 6.022 x 1023particles

Ptotal = P1+ P2+ P3+ … + Pi

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

3. The mass percentage composition of dry air at sea level is

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

 Comes in different forms:

 Cannot be evaluated without knowledge of path

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

 Its transfer is irreversible, which can only be from a body of high

where C is the heat capacity (quantity of heat needed to raise

MatSciPhyChem Engr. SuzzydTE

 It is the measure of responsiveness of the system to the difference in

 The ratio of the energy input to temperature increase depends strongly

MatSciPhyChem Engr. SuzzydTE

• Specific Heat Capacity – amount of heat required to increase the

• Molar Heat Capacity – amount of heat required to increase the

MatSciPhyChem Engr. SuzzydTE

 At constant P, the same amount of heat is required to raise the

MatSciPhyChem Engr. SuzzydTE

 For monoatomic ideal gas:

MatSciPhyChem Engr. SuzzydTE

Q  nCT C = molar heat capacity

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

At constant pressure, H = nCpT

When Cp is not constant, it can be expressed as: p 2

MatSciPhyChem Engr. SuzzydTE

 Enthalpies of Physical Change

Given the following heats of formation:

 Entropy is an extensive property of the system as it depends on the

 In addition, entropy is a state function.

 Clausius coined the term "entropy" to refer to the dissipated potential.

MatSciPhyChem Engr. SuzzydTE

a. CaCO3(s)  CaO(s) + CO2(g)

MatSciPhyChem Engr. SuzzydTE

 For an irreversible process, the sum of the entropy change of the

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE

MatSciPhyChem Engr. SuzzydTE