THERMODYNAMIC

Thermodynamic is the branch for Surroundings

physical chemistry concerned with Barrier

the study of the transformations of
energy.

System

Universe

Biological thermodynamics and/or bioenergetics is the

quantitative study of the energy transduction that occur in and
between living organisms, structures and of the nature.
 Thermodynamics – System and
Surrounding
A system is defined as the matter within a defined region of
space (i.e reactant, product, human, universe).

The surrounding are where we make our observation or the rest

of the universe.

We need to distinguish three types of the system;

a) An open system
b) A closed system
c) An isolated system
 Thermodynamics – System and
Surrounding
An open system can exchange both energy and matter with its
surroundings and hence can undergo changes of composition.

An example of an open system – a biological cells, living

organisms including human.

Mass Out

Open Energy Out

Energy In
System

Mass In
 Thermodynamics – System and
Surrounding
A closed system is a system that can exchange energy but not
matter with its surrounding.

An example of an close system – electrical devices.

Close Energy Out

Energy In
System
Mass
 Thermodynamics – System and
Surrounding
An isolated system is a system that can exchange neither
energy nor matter with its surrounding.

An example of an isolated system – insulated electrical devices.

Energy
Isolate
System
Mass
 The First Law of Thermodynamic

The Principle of Energy Conservation

(The energy is conserved)

The energy can be changed from one form to another (i.e

potential energy to kinetic energy) but it cannot be created or
destroyed.

The total amount of energy in the universe remains constant,

although the form of energy may change.
 The First Law of Thermodynamic

The first Law of Thermodynamics for an open system states

that the changes in the internal energy of a system is equal to
the amount of energy added to the system by matter (flowing
in and by heating, minus the amount lost by matter flowing
out) and in the form of work done by the system.

ΔU = Q + W
ΔU is the change in internal energy (J)
Q is the heat energy supplied to the system (J)
W is the work done on the system (J)
 The First Law of Thermodynamic

The first Law of Thermodynamics for the closed system states

that the changes of internal energy of the system equals to the
amount of heat added to the system minus the work done by
the system.

ΔU = Q - W
ΔU is the change in internal energy (J)
Q is the heat energy supplied to the system (J)
W is the work done by the system (J)
 The First Law of Thermodynamic
The internal energy (U) is the term used to describe all of the
energy contained in a system and it is given a symbol, U.

There are two forms of energy that can make up the internal
energy of a system;

Potential energy – this is an energy stored in the stretched or

compressed bonds between the molecules of a system.

Kinetic energy – this is an energy due to a motion of

molecules (translational, rotational or vibrational).
 The First Law of Thermodynamic
U is a state function, its value depend only on the current
state of the system.

We do not know and cannot measure the total internal

energy (U) because it includes the kinetic and potential
energies of all the components of the system.

**Only ΔU can be measured directly**

However there is no problem with dealing

with the changes in internal energy (ΔU).
 The First Law of Thermodynamic
ΔU for biological system = Q + W

Heat (Q) is a form of energy associated with the motion of

molecule and capable of being transmitted by thermal
interaction.

The unit of heat (Q) most commonly employed in biological

system is the kilocalorie (kcal) or calorie (cal).

1 joule (J) = 0.239 calorie (cal)

1 kilocalorie (kcal) = 4186. 8 joule (J)
 The First Law of Thermodynamic

The amount of heat energy needed to increase

the temperature of 1 kg of the material by 1 0C.

C = Q/mΔθ

C is the specific heat capacity (J.kg-1.0C-1 or J.kg-1.K-1)

Q is the heat energy supplied (J)
m is the mass of material (kg)
Δθ is the change in temperature (0C or K) = final T – initial T
 The First Law of Thermodynamic
ΔU for biological system = Q + W

Work (W) is defined as the work expanded by a force of one

Newton through a distance of one metre (J).

W = Fx

W is the work done (J)

F is the force applied (N)
X is the distance moved (m)
 Exam Hint
Decide and write down the
signs of work done and
energy before using the
ΔU for biological system = Q + W values in The First Law of
Thermodynamics

Energy is supplied into a system, making Q value is +ve

Energy is removed from a system, making Q value is –ve

Doing work on the system, making W value is +ve

System does work on surrounding, making W value is -ve

 Exam Hint
ΔU for biological system = Q + W

Energy (Internal energy, heat, work) – Joules (J)

Time – second (s)

Volume – m3 To avoid making errors with unit of

values used in calculations, it is best
Temperature - Kelvin to change all units into standard
units (SI) before starting any
calculations.
1st LAW OF THERMODYNAMICS

Question 1

A student scrubbing the inside of fridge. As he scrubs, he

is applying the force through a distance and performing
50 J of work on the interior of the fridge. At the same
time the interior of the fridge is being cooled and has had
30 J of heat energy removed. Calculate the internal
energy change of fridge interior if any.
Step 1 List all known values

Q = -30 J (The heat energy is removed from the fridge interior)

W = +50 J (The work being done on the fridge interior)

Step 2 List all unknown values

ΔU

Step 3 Apply known values

ΔU = (-30 J) + (+50 J)
= -30 J + 50 J
= 20 J
1st LAW OF THERMODYNAMICS

Question 2

What is the change in internal energy of a system when a

total of 150 J of heat transfer occurs out of the system
and 159 J of work is done on the system.
Step 1 List all known values

Q = -150 J (The energy is removed from the system )

W = +159 J (The work being done on the system )

Step 2 List all unknown values

ΔU

Step 3 Apply known values

ΔU = (-150 J) + (+159 J)
= -150 J + 159 J
=9J
1st LAW OF THERMODYNAMICS

Question 3

Suppose there is heat transfer of 4 x 10-2 kJ to a system,

while the system does 10 J of work. Later there is heat
transfer of 25 J out of the system while 4 J of work is
done on the system. What is the net change in internal
energy of the system?
Step 1 List all known values

Q = 40 J – 25 J (The net energy is supplied into the system )

W = -10 J + 4 J (The net work being done on the system )

Step 2 List all unknown values

ΔU

Step 3 Apply known values

ΔU = (+15 J) + (-6 J)
= 15 J - 6 J
=9J
1st LAW OF THERMODYNAMICS

Question 4

Suppose a woman does 500 J of work and 9500 J of heat

transfer occurs into the environment in the process.
What is the increase or decrease in her internal energy,
assuming no change in temperature and consumption of
food?
1st LAW OF THERMODYNAMICS

Question 5

How much heat transfer occurs from a man if his internal

energy decreased by 150 J while he was doing 30 J of
work?
The Second Law of Thermodynamic
The Principle of Entropy or Disorder
(Entropy is a measure of disorder or the amount of energy
which is unavailable to do work)

The Second Law of Thermodynamic stated that the entropy or

the degree of disorder is always increasing in the universe.
The Second Law of Thermodynamic
 The Second Law of Thermodynamic
Thermal energy/heat (Joules) – is kinetic energy in transit
from object to another due to temperature gradient.

Temperature (Degrees) – is the average kinetic energy of

particles in an object and not the total amount of kinetic
energy of the particles.

Temperature #1 Temperature #2

Heat
 The Zeroth Law of Thermodynamic
The Zeroth Law of Thermodynamic stated that if two systems
are separately found to be in thermal equilibrium with a third
system, the first two system are in thermal equilibrium with
each other.

Thermal equilibrium – a state in which two substances in

physical contact with each other exchange no heat energy.

Object #1
(Thermometer)

Object #1 Object #2 Object #2 Object #3

 Thermal Capacity
Thermal capacity = heat capacity

Specific heat capacity is the amount of heat energy required to

raise the temperature of a body per unit of mass.

Specific heat capacity is the amount of heat energy required to

increase the temperature of 1 kg of the material by 1 0C.

In SI unit – specific heat capacity (symbol c) is the amount of

heat in joules required to raise 1 gram of a substance by 1
Kelvin.
 Thermal Capacity

c = Q / mΔϴ

c is specific heat capacity (J.g-1.0C-1 or J.g-1.K-1)

Q is heat energy supplied (J)

m is mass of material (g)

Δθ is change in temperature (0C or K)

= Final T – Initial T
 Thermal capacity

Question 1

Calculate how much energy is required to increase the

temperature of 2 kg of water from 20 0C to boiling point,
100 0C? Given specific heat of water, 4.184 J.g-1. 0C
Step 1 List all known values

m = 2000 g

Δϴ = 100 0C – 20 0C = 80 0C

c = 4.184 J.g-1. 0C-1

Step 2 List all unknown values

Q
Step 3 Apply known values

Q = mc Δϴ
Q=?
Q=?
 Thermal capacity

Question 2

A student must use 225 ml of hot water in a lab

procedure. Calculate the amount of heat required to
raise the temperature of 225 ml of water from 20 0C to
100 0C . Specific heat for water = 4.184 J.g-1. 0C
Step 1 List all known values

m = 225 ml = 225 g

Δϴ = 100 0C – 20 0C = 80 0C

c = 4.184 J.g-1. 0C-1

Step 2 List all unknown values

Q
Step 3 Apply known values

Q = mc Δϴ
Q=?
Q=?
 Thermal capacity

Question 3

Calculate the specific heat capacity of biological waste if

a 15.4 g waste absorbs 393 J when it is heated from 0 to
37.6 0C?
Step 1 List all known values

m = 15.4 g

Δϴ = 37.6 0C – 0 0C

Q = 393

Step 2 List all unknown values

c
Step 3 Apply known values

Q = mc Δϴ
c=?
c=?
 Thermal capacity

Question 4

A 40 g sample of protein X releases 2952 J as it cools

from 50 0C. Calculate the final temperature of the protein
X (specific heat capacity for protein X = 2.46 J.g-1. 0C )
Step 1 List all known values

m = 40 g

Q = -2952 J

T1 = 50 0C

Step 2 List all unknown values

?
Step 3 Apply known values

Q = mc Δϴ
 ENTHALPY

Enthalpy (H) is a measure of total energy of a thermodynamic

system.

It includes the internal energy, which is the energy required to

create a system, and the amount of energy required to make
room for it by displacing its environment and establishing its
volume and pressure.

Original definition;
The heat change which occurs when 1 mol of the substance
reacts completely with oxygen to form a product at 298 K and
1 atm.
 Enthalpy
• Enthalpy (H) is a measure of total energy in the system.

• Mathematically;

H = U + PV ΔH = ΔU + PV

Where:

» H is the enthalpy (joules)

» U is the internal energy (joules)

» P is the pressure of the system (pascals or atm)

» V is the volume (cubic metres, m3)

 Enthalpy
• Enthalpy change is defined by the following equation:

ΔH = Hfinal - Hinitial

Where:

» ΔH is the enthalpy change (J)

» Hfinal is the final enthalpy of the system, measured in
joules. In a chemical reaction, Hfinal is the enthalpy of
the product (J)
» Hinitial is the initial enthalpy of the system, measured
in joules. In a chemical reaction , Hinitial is the
enthalpy of the reactants (J)
 Enthalpy
• Enthalpy change is defined by the following equation:

ΔH = Hproducts - Hreactants

Where:

» ΔH is the enthalpy change (J)

» Hproducts is the enthalpy of the product (J)

» Hreactants is the enthalpy of the reactants (J)

 Enthalpy

Example 1:

Calculate the ΔH value of the reaction;

HCl + NH3 → NH4Cl

(ΔH values for HCl is -92.30 J/mol; NH3 is -80.29 J/mol;

NH4Cl is -314.4 J/mol)
 Enthalpy

Answer:

HCl + NH3 → NH4Cl

ΔH = Hproducts - Hreactants

Hproducts = (1 mol )( -314.4 J/mol)

Hreactants = (1 mol)(-92.30 J/mol) + (1 mol)(-80.29 J/mol)

ΔH = ?
 Enthalpy

Example 2:

Calculate the ΔH value of the reaction;

2C8H18 + 25O2 → 16CO2 + 18H2O

(ΔH values for C8H18 = 15.7 kJ/mol, O2 = 9.8 kJ/mol, CO2 =

11.8 kJ/mol and H2O = 18.3 kJ/mol)
 Enthalpy

Answer:

2C8H18 + 25O2 → 16CO2 + 18H2O

ΔH = Hproducts - Hreactants

Hproducts = (16 mol)(11.8 kJ/mol) + (18 mol)(18.3 kJ/mol)

Hreactants = (2 mol)(15.7 kJ/mol) + (25 mol)(9.8 kJ/mol)

ΔH =
 Enthalpy
We can also determine ΔH for a
reaction based on bond dissociation
energy.

Breaking bonds requires energy while

forming bonds releases energy.

In a given equation, we need to

Use this information to calculate the
amount of energy used to break the
bonds and the amount used to form
the bonds.
determine what kind of bonds are
broken and what kind of bonds are
formed.

When we subtract the amount to

break the bonds with the amount to
form the bonds, we actually
calculate the ΔH of the reaction.
 Enthalpy

Example:

Calculate the ΔH value of the reaction;

A2 + 3B2 → 2AB3

(The bond dissociation energy for A-A is 163 kJ/mol; B-B is

436 kJ/mol; A-B is 391 kJ/mol)
 Enthalpy
Answer:

A2 + 3B2 → 2AB3

To use the bond dissociation energies, we must determine

how many bonds are in the products and the reactants.

• In A2 there is 1 A-A bond

• In 3B2 there are 3 B-B bonds

• In 2AB3 there are 6 A-B bonds

 Enthalpy

Answer:

A2 + 3B2 → 2AB3

ΔH = Hproducts - Hreactants

Hproducts = 6(391) = 2346

Hreactants = 163 + 3(436) = 1471

ΔH = 2346 - 1471 = 875 kJ/mol

Enthalpy

Spontaneous reaction
• ΔH = -ve (Exothermic)
Non-spontaneous reaction
• ΔH = +ve (Endothermic)
 Entropy
• Entropy is a measure of the disorder of the system.

ΔS = Sfinal - Sinitial

Where:

» ΔS is the entropy change (J)

» Sfinal is the final entropy of the system, measured in
joules. In a chemical reaction, Sfinal is the entropy of
the product (J)
» Sinitial is the initial entropy of the system, measured
in joules. In a chemical reaction , Sinitial is the entropy
of the reactants (J)
 Entropy
• Entropy is a measure of the disorder of the system.

ΔS = Sproducts - Sreactants

Where:

» ΔS is the entropy change (J)

» Sproducts is the entropy of the product (J)
» Sreactants is the entropy of the reactants (J)
 Entropy

Example 1:

Calculate the ΔS value of the reaction;

HCl + NH3 → NH4Cl

(ΔS values for HCl is -92.30 J/mol; NH3 is -80.29 J/mol;

NH4Cl is -314.4 J/mol)
 Entropy

Example 2:

Calculate the ΔS value of the reaction;

2C8H18 + 25O2 → 16CO2 + 18H2O

(ΔS values for C8H18 = 15.7 kJ/mol, O2 = 9.8 kJ/mol, CO2 =

11.8 kJ/mol and H2O = 18.3 kJ/mol)
 Gibb’s Free Energy

The free energy of a system, that is free to do a work at

constant temperature and pressure.

G = H - TS

Where;
G = is the free energy (J)
H = is the enthalpy (J)
T = is the temperature (K)
S = is the entropy (J)
 Gibb’s Free Energy
• We can calculate the changes in free energy (ΔG);

ΔG = Gfinal - Ginitial
ΔG = Gproducts - Greactants
Spontaneous reaction
• ΔG = -ve (Exothermic)
Non-spontaneous reaction
• ΔG = +ve (Endothermic)

T must be in K and not 0C

ΔG = ΔH - TΔS Eg: 50 0C
50 0C + 273.15 = 323.15 K
 Gibb’s Free Energy

Example :

Calculate the ΔG value of the reaction at 73 0C;

2C8H18 + 25O2 → 16CO2 + 18H2O

(ΔH values for C8H18 = 15.7 kJ/mol, O2 = 9.8 kJ/mol, CO2 =

11.8 kJ/mol and H2O = 18.3 kJ/mol)

(ΔS values for C8H18 = 10.8 kJ/mol, O2 = 5.4 kJ/mol, CO2 =

7.8 kJ/mol and H2O = 15.9 kJ/mol)
Thermal Energy Transfer

Convection Energy transfers occurs with the

transfer of mass!!!!

The transfer of energy as heat can take

place via…..

Radiation Conduction

Energy transfers occurs without the transfer

of mass!!!!
Thermal Energy Transfer
 CONDUCTION
Conduction is a transport of thermal energy through an object
by a series of collisions between adjacent atoms, molecules or
electrons.

direction of energy flow The energy from the bunsen burner causes the
molecules in the metal rod to move faster, increasing
the rate and size of their vibrations.

These molecule transfer some of their extra kinetic

energy to neighbouring molecules.

Therefore, the temperature of entire metal rod

increases.

How rapidly an object transports thermal energy by conduction

(thermal conductivity) depends, in part, on what material the
object is made of.
CONDUCTION

 Thermal  Contact  Temperature 

   
 Rate of   Conductivity  Area  Difference 
  
 Heat Flow  Thickness 

Q A
Thermal Conduction Equation
 T
t d
 CONVECTION
Convection is the transfer of thermal energy due to the motion
of the substance (most commonly fluid; liquid or gas) that
contain the thermal energy.

As a fluid is heated, the atoms and molecules of

the fluid move faster, spread out and become less
dense.

This heated and less dense fluid will rise via a

buoyant force from the surrounding cooler and
more dense fluid.

The heated fluid continues to rise until it has

cooled (by transferring its thermal energy to the
rest of the fluid), becomes more dense than the
surrounding fluid, and falls back to the heat
source, at which point a convection cycle will
begin
 RADIATION
Radiation (electromagnetic radiation) is the transfer of thermal
energy by emission as particles or waves.

No medium is needed such as air or

water, for the radiation to travel and
transfer of thermal energy.

By radiation, thermal energy can

passed through a perfect vacuum, as
energy from the sun does in reaching
earth.

Examples: visible light, infrared

radiation, microwaves, ultraviolet etc.
 THERMAL ENERGY TRANSFER
EQUATION

Q = m  Cp  ΔT
Q = energy transfer (Joules)
m = mass of the material (kilograms)
Cp = specific heat capacity of the material (J / kg C )
T = temperature
Δ = difference
 THERMAL ENERGY TRANSFER
EQUATION
Q P = rate of energy transfer (Watts)
P= Q = energy transfer (Joules)
Δt
t = time (seconds)
ΔT k = thermal conductivity
P = kA
L A = area of thermal conductivity
L = thickness of material
PL
k= T = temperature
AΔT Δ = difference
 CALCULATING ENERGY TRANSFER
Calculate the energy transferred when a block Qof
aluminum at 80.0°C is placed in 1.00 liter (1kg) of water
at 25.0°C if the final temperature becomes 30.0°C.
Step 1 List all known values

Mass of water = 1 kg
J
Cp of water = 4184 kg ×o C

Difference in temperature = ΔT = 30.0°C – 25.0°C = 5.0°C

J
Cp of Al = 900. kg ×o C

Difference in temperature = ΔT = 80.0°C – 30.0°C = 50.0°C

 Calculating Energy Transfer
Step 2. List all unknown values
Q = energy transferred
mAl = mass of the Al block

Step 3. Select equations to solve unknown values

Q = m  Cp  ΔT QAl = Qwater

Step 4. Solve for Qwater

J
Qwater = (1.00kg) • 4184 o
 5.0 C = 21, 000 J gained
o

kg× C
 Calculating Energy Transfer
Step 5. Solve for mAl

QAl (lost) = Qwater (gained) = 20,920 J

QAl = mAl  Cp  ΔT
QAl 20,920J
m Al = =
Cp  ΔT 900. J  50.0o C
o
kg C

mAl = 0.46 kg = 460g

 Calculating Energy Transfer
Calculate the energy transfer in a wall section
measuring 2m by 1m by 0.04m thick with a Q
J
thermal conductivity of 0.10 s× m×°C . Opposing
sides of the wall section have a temperature of
10°C and 5°C after one hour.
Step 1. List all known values
Area of thermal conductivity = A = 2m * 1m = 2m2
J
Thermal conductivity = k =0.10 s× m×o C

Thickness of material = L = 0.04m

Difference in temperature = ΔT = 10°C - 5°C = 5°C

Difference in time = Δt = 1 hour = 3600s

 Calculating Energy Transfer
Step 2. List all unknown values
P = Rate of energy transfer
Q = Energy transfer

Step 3. Select equations to solve unknown values

Q ΔT
P= P = kA
Δt L
Step 4. Solve in terms of Q
Q = P • Δt
Step 5. Combine equations
ΔT
Q = (kA ) • Δt
L
 Calculating Energy Transfer
Step 6. Apply known values

ΔT
Q = (kA ) • Δt
L
 2   5°C  
Q    0.10 s× m×°C • 2m  •  0.04m   • 3600s
J
   

Q = 90,000J