Kimia Fisika II: Universitas Negeri Semarang

Universitas Negeri Semarang
Kimia Fisika II
Sri Kadarwati, Ph.D

Endah Fitriani Rahayu, M.Sc.
Programme Learning Outcomes
Attitude:
1. Working in a team, showing a high social awareness and empathy
towards society and environment.
2. Internalise the academic values, norms, and ethics.
3. Showing independent responsibilities for their expertise.
4. Internalise appreciative and awareness attitudes in conserving the
environment and the developed socio-cultural values in the society.
General skills:
5. Capable to apply logical, critical, systematic, and innovative thoughts in
developing or implementing science and technology in accordance with
humanistic values and expertise.
6. Capable to prove the independent, high-qualified and measurable work.

Specific skills:
1. Capable to effectively communicate the information, ideas, arguments in various
media based on the results of a study to the society.
2. Capable to implement the conservation values in the society.

Knowledge learning outcomes:
Capable to solve Science-and-technology-related problems in general chemistry fields
and in simple scopes such as identifying and analysing organic and inorganic
compounds, as well as the analysis using a certain method of analysis and the
application of relevant technologies.
TOPICS
BEING
DISCUSSED
Physical Chemistry II covers:
spontaneity and equilibrium;

systems with variable composition and their equilibrium
states;
phase equilibria in a simple system;
Ideal solution and colligative properties;
ideal solution of multi-components;
equilibria between condensed phases;
equilibria in non-ideal systems;
equilibria in electrochemical cells;
Surface phenomena
You will discuss/learn
about:
Spontaneity and equilibrium;
Systems with variable composition
and their equilibrium states;
Phase equilibria in a simple system;
Ideal solution and colligative
properties; With Bu Srika
Ideal solution of multi-components;
With Bu Endah
You will discuss/learn about:
Equilibria between condensed phases;

Equilibria in non-ideal systems;
Equilibria in electrochemical cells;
Surface phenomena
Assessment:
Assignments with case method
Mid-semester exam
Students’ attendance during
discussion
Students’ involvement during
discussion
Text books
https://drive.google.com/file/d/1-
01 LtkhuzeSioQ2QyEQhV8T9-
vmRCHHcw8/view?usp=sharing
02 Other available literatures

Please drop your questions
Chemical Thermodynamics
An overview
The chemistry that deals with the energy

and entropy changes and the spontaneity
of a chemical process.
First Law of Thermodynamics
 The change in the internal energy (DE) of a
thermodynamic system is equal to the
amount of heat energy (q) added to or lost by
the system plus work done (w) on or by the
system.
DE = q + w
 For work that only involves gas expansion

or compression, w = -pDV;
Values of Thermodynamic Functions
• FLoT: DE = q + w;
 q is assigned a positive value if heat is absorbed, but a negative

value if heat is lost by the system;
 w is assigned a positive value if work is done on, but a negative

value if work is done by the system.
 For processes that do not involve phase changes, positive DE results

in temperature increase.
Second Law of Third Law of
Thermodynamics Thermodynamics
Energy tends to flow from a The entropy of a perfect
high energy concentration to a crystalline substance is zero at
dispersed energy state; absolute zero temperature (0.0 K)
Energy dispersion or diffusion
is a spontaneous process. Is absolute zero temperature
Dispersed or diffused energy is achievable?
called entropy
According to SLoT, a
process/reaction is spontaneous
if the entropy of the universe
(system + surrounding)
increases.
What is What is the significance of
ENTROPY? entropy?
 A thermodynamic (energy)
function that describes the
degree of randomness or  Nature spontaneously proceeds toward
probability of existence.
the state that has the highest probability
 As a state function –
of (energy) existence – highest entropy
entropy change depends  Entropy is used to predict whether a
only on the initial and
given process/reaction is
final states, but not on how
thermodynamically possible;
the change occurs.
Entropy:
which are most probable?
Relative Entropy of Substances
Entropy:
 increases from solid to liquid to vapor/gas;

 increases as temperature increases;
 of gas increases as its volume increases at constant temperature;
 increases when gases are mixed.
 of elements increases down the group in the periodic table;
 of compound increases as its structure becomes more complex.
Where do molecules have the higher entropy
o
Standard Entropy, S
• The entropy of a substance in its most stable state at 1 atm and
25oC.
• The entropy of an ionic species in 1 M solution at 25oC.
Entropy and Second Law of
Thermodynamics
• Thesecond law of thermodynamics states that all spontaneous
processes are accompanied by increase in the entropy of the
universe.
 Universe = System + Surrounding;
 System: the process/reaction whose thermodynamic change is being

studied;
 Surrounding: the part of the universe that interacts with the system.
Conditions for Spontaneous Process
• Entropy change for a process:
• DSuniv = DSsys + DSsurr > 0,  process is spontaneous
DSuniv = DSsys + DSsurr = 0,  process is at equilibrium
• If DSsys < 0, DSsurr > 0, and |DSsurr| > |DSsys|

• If DSsurr < 0, DSsys > 0, and |DSsys| > |DSsurr|
Gibb’s Free Energy
• For spontaneous reactions,
DSuniv = DSsys + DSsurr > 0
DSsurr = -DHsys/T
DSuniv = DSsys - DHsys/T
-TDSuniv = DGsys = DHsys - TDSsys < 0
DGsys is called Gibb’s free energy

• A new criteria for spontaneous process is DGsys < 0
What is Free Energy?
Thermodynamic Free Energy
• It
is the maximum amount of chemical energy derived from a
spontaneous reaction that can be utilized to do work or to drive a
nonspontaneous process.
• It
is the minimum amount of energy that must be supplied to make a
nonspontaneous reaction occur.
Effect of Temperature on DG and Spontaneity
——————————————————————————————————
DH DS T DG Comments Examples
——————————————————————————————————
• - + high - spontaneous at 2H2O2(l)  2H2O(l) + O2(g)
• or low all temperature
• + + high - spontaneous at CaCO3(s)  CaO(s) + CO2(g)
• high temperature
• - - low - spontaneous at N2(g) + 3H2(g)  2NH3(g)
• low temperature
• + - high + nonspontaneous at 2H2O(l) + O2(g)  2H2O2(l)
• or low all temperature
________________________________________________________
Entropy Change in Chemical Reactions
• At constant temperature and pressure,
DSorxn = SnpSoproducts – SnrSoreactants
• In general, DSorxn > 0 if Snp > Snr
• Example-1:
• C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(g), (Snp > Snr)
DSorxn = {(3 x SoCO2) + (4 x SoH2O)} – {(SoC3H8) + (5 x SoO2)}
• = {(3 x 214) + (4 x 189)}J/K – {270 + (5 x 205)}J/K
• = (642 + 756) J/K – (270 + 1025) J/K
= 103 J/K
Entropy Change in Chemical Reactions
DSorxn < 0 if Snp < Snr
• Example-2:
• CO(g) + 2H2(g)  CH3OH(g), (Snp < Snr)

DSorxn = (SoCH3OH) – {(SoCO) + (2 x SoH2)}
• = 240 J/K – {198 J/K + (2 x 131 J/K)
• = 240 J/K – 460 J/K = -220 J/K
Effect of Temperature on DGo
DGo = DHo – T DSo
• Example-1:
• For the reaction: N2(g) + 3H2(g)  2NH3(g),
DHo = -92 kJ and DSo = -199 J/K = -0.199 kJ/K
• At 25oC, T DSo = 298 K x (-0.199 J/K) = -59.3 kJ
• DGo = DHo – T DSo = -92 kJ – (-59.3 kJ) = -33 kJ;
•  reaction is spontaneous at 25oC
• At 250oC, T DSo = 523 K x (-0.199 J/K) = -104 kJ;
• DGo = DHo - TDSo = -92 kJ – (-104 kJ) = 12 kJ;
•  reaction is nonspontaneous at 250oC
Effect of Temperature on DGo
DGo = DHo – TDSo
• Example-2:
• For the reaction: CH4(g) + H2O(g)  CO(g) + 3H2(g),
DHo = 206 kJ and DSo = 216 J/K = 0.216 kJ/K
• At 25oC, TDSo = 298 K x (0.216 J/K) = 64.4 kJ
• DGo = DHo - TDSo = 206 kJ – 64.4 kJ = 142 kJ;
• reaction is nonspontaneous at 25oC.
• At 1200 K, TDSo = 1200 K x (0.216 J/K) = 259 kJ;
• DGo = DHo - TDSo = 206 kJ – 259 kJ) = -53 kJ;
• reaction is spontaneous at 1200 K
DG under Nonstandard Conditions
• Free energy change also depends on concentrations and partial pressures;
• Under nonstandard conditions (Pi not 1 atm),
DG = DGo + RTlnQp,
Consider the reaction: N2(g) + 3H2(g)  2NH3(g),
Qp =
Under standard condition, PN2 = PH2 = PNH3 = 1 atm, Qp = 1;

ln Qp = 0, and DG = DGo
DG of reaction under nonstandard condition
Consider the following reaction at 250 oC:
N2(g) + 3H2(g)  2NH3(g),
where, PN2 = 5.0 atm, PH2 = 15 atm, and PNH3 = 5.0 atm
Qp = 52/(5 x 153) = 1.5 x 10-3
lnQp = ln(1.5 x 10-3 ) = -6.5
Under this condition, DG = DGo + RTlnQp;
(For this reaction at 250oC, calculated DGo = 12 kJ)
 DG = 12 kJ + (0.008314 kJ/T x 523 K x (-6.5))
= 12 kJ – 28 kJ = -16 kJ  spontaneous reaction
Transition Temperature
• Thisis a temperature at which a reaction changes from being
spontaneous to being nonspontaneous, and vice versa, when Qp or Qc
equals 1 (standard condition)
• Attransition temperature, Tr,
DGo = DHo – TrDSo = 0;  Tr = DHo/DSo
For reaction: N2(g) + 3H2(g)  2NH3(g),

Tr = -92 kJ/(-0.199 kJ/K) = 460 K = 190oC
Under standard pressure (1 atm), this reaction is spontaneous below
190oC, but becomes nonspontaneous above this temperature.
Transition Temperature
• For reaction: CH4(g) + H2O(g)  CO(g) + 3H2(g),
DHo = 206 kJ and DSo = 216 J/K = 0.216 kJ/K
DGo = DHo + TrDSo = 0,
Tr = 206 kJ/(0.216 kJ/K) = 954 K = 681 oC
Under standard pressure (1 atm), this reaction is not spontaneous below

681oC, but becomes spontaneous above this temperature.
Reactions with both DHo and DSo < 0 favor low temperature;
Those with both DHo and DSo > 0 favor high temperature.
Free Energy and Equilibrium Constant
• For spontaneous reactions, DG decreases (becomes less negative) as the
reaction proceeds towards equilibrium;
• At equilibrium, DG = 0;
• DG = DGo + RTlnK = 0
• DGo = -RTlnK
• lnK = -DGo/RT (DGo calculated at temperature T)
-(DGo/RT)
• Equilibrium constant, K = e
DGo < 0, K > 1; reaction favors products formation
DGo > 0, K < 1; reaction favors reactants formation
DGo = 0, K = 1; reaction favors neither reactants nor products
Calculating K from DGo
• Consider the reaction: N2(g) + 3H2(g)  2NH3(g),
• At 25oC, DGo = -33 kJ

• lnK = -(-33 x 103 J/(298 K x 8.314 J/K.mol)) = 13
• K = e13 = 4.4 x 105 (reaction goes to completion)
• At 250oC, DGo = 12 kJ;

• lnK = -(12 x 103 J/(523 K x 8.314 J/K.mol)) = -2.8
• K = e-2.8 = 0.061 (very little product is formed)
Assignment 1
• Please access the assignment 1 through
https://forms.gle/YKRx9ke5bYmrfDt49
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Universitas Negeri Semarang

Sri Kadarwati, Ph.D

6. Capable to prove the independent, high-qualified and measurable work.

spontaneity and equilibrium;

Equilibria between condensed phases;

02 Other available literatures

The chemistry that deals with the energy

 For work that only involves gas expansion

 q is assigned a positive value if heat is absorbed, but a negative

 w is assigned a positive value if work is done on, but a negative

 For processes that do not involve phase changes, positive DE results

 increases from solid to liquid to vapor/gas;

 Universe = System + Surrounding;

 System: the process/reaction whose thermodynamic change is being

• If DSsys < 0, DSsurr > 0, and |DSsurr| > |DSsys|

DGsys is called Gibb’s free energy

DSorxn < 0 if Snp < Snr

• CO(g) + 2H2(g)  CH3OH(g), (Snp < Snr)

Under standard condition, PN2 = PH2 = PNH3 = 1 atm, Qp = 1;

For reaction: N2(g) + 3H2(g)  2NH3(g),

Under standard pressure (1 atm), this reaction is not spontaneous below

• At 25oC, DGo = -33 kJ

• At 250oC, DGo = 12 kJ;

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