THERMODYNAMICS

AND HEAT TRANSFER

MODULE - 1
SCOPE OF THERMODYNAMICS

• Thermos – meaning heat

• Dynamis – Force or power
• Study of heat and its relationship with work, energy and power; energy
and its transformation
• Criteria for equilibrium – direction in which changes takes place
• Doesn’t say anything about the resistance
Driving force
Rate 
R esistance
TERMINOLOGIES

• System – Part of the universe being studied or observed

• Surroundings – Rest of the universe
• Open System – Both heat and Mass transfer
• Closed system – No Mass Transfer, Only Heat Transfer
• Isolated System – Neither heat nor mass are transferred
TERMINOLOGIES

• Homogeneous System – also called phase. Properties are same

throughout or properties vary smoothly without showing any surface of
discontinuity
• Heterogeneous System – 2 or more homogeneous system. Properties
vary sharply at the phase boundaries.
• Process – Changes taking place within the system
• State – Condition of a system defined by specifications
TERMINOLOGIES

• Properties – Variable used to define the state of the system

• Intensive – Size independent. Eg: Temperature, Pressure
• Extensive – Size dependent. Eg :Volume
• State Functions – depends only on the end states
• Path Functions – depends on the path followed to reach a state
• Steady State – Properties at a specified location do not vary with
time
TERMINOLOGIES

• Equilibrium – Properties are uniform throughout.

• Thermal Equilibrium
• Mechanical Equilibrium
• Chemical Equilibrium
---- All three satisfied – THERMODYNAMIC EQUILIBRIUM
• Reversible Process – Process can be reversed without any change in
surroundings. Driving force is infinitesimal in magnitude.
• Irreversible Process – Finite driving force.
TERMINOLOGIES

• Heat Reservoir – Sufficiently large system in stable

equilibrium from which a finite amount of heat can be
transferred without change in its T – HTR & LTR
• Heat Engine – from which heat is transferred
• Heat Pump – to which heat is transferred
COEFFICIENT OF PERFORMANCE

W Q2
   
Q1 W
LAWS OF
THERMODYNAMICS
ZEROTH LAW OF THERMODYNAMICS

• If a body A is in thermal equilibrium with B

and B is in thermal equilibrium with C, then
C is also in thermal equilibrium with A.
• Temperature – degree of hotness or
coldness of an object.
FIRST LAW OF THERMODYNAMICS

• Also known as the Law of conservation of energy.

• States that although energy may be converted from one form to
another, it can neither be created nor be destroyed.
• First Law of TD for a cyclic process
• What is a Cyclic process?
• First law tells that the Algebraic summation of all work effects equals the
summation of all heat effects.
FIRST LAW FOR A CYCLIC PROCESS

W   Q
If units of heat and work are different
W  J  Q
J is the mechanical equivalent of heat if work is mechanical,
J is the electrical equivalent of heat if work is electrical etc
INTERNAL ENERGY

• Energy stored in the system by virtue of the configuration and motion of

molecules constituting the system, denoted by U.
• Molecules in system possess
• kinetic energy of translation, rotation and vibration.
• Potential energy due to forces of attraction.
• Internal energy is the sum of both.
• For a cyclic process, Internal energy remains same. Thus ∆U = 0.
• For a non-cyclic process ∆U = Q - W
FIRST LAW FOR NON CYCLIC NON FLOW
PROCESS
• Heat and work effects are not equal – some energy gets stored/removed from the system –
these changes are measured as the change in internal energy.
• Whatever changes occurs in the system, the opposite change occurs in the surroundings

( E ) surr  ( E ) sys  Q  W
 ( E ) sys   ( KE )   ( PE )  U
If changes in KE and PE are negligible
 ( E ) sys  U  Q  W
For differenti al changes
dU  dQ  dW
ENTHALPY

• Total Energy of the system which includes the internal energy and the energy stored in
the system due to the expansion possibilities of the system.
dH  dU  d ( PV )
Since all the terms are state functions, On integration
H  U   (PV)
For a mechanically reversible non flow process at constant P
dH  dU  PdV  VdP
dH  dQ  dW  PdV  VdP
dH  dQ  PdV  PdV  VdP
dH  dQ
FIRST LAW FOR FLOW PROCESS
 FIRST LAW FOR FLOW PROCESS

By First Law of TD,

U 1  gZ 1  P1V1  12 u12  Q  W s  U 2  gZ 2  P2V2  12 u 22
 U   ( PV )  gZ  12 u 2  Q  W s
 H  gZ  12 u 2  Q  W s
Assuming the KE and PE terms are negligibly small
H  Q  Ws
LIMITATIONS OF THE FIRST LAW OF
THERMODYNAMICS

• Inability to deal with the direction of the process and

the extent of change.
• Fails to recognize the qualitative differences between
various forms of energy.
SECOND LAW OF THERMODYNAMICS

• All the spontaneous processes are to some extent irreversible and accompanied by a
degradation of energy.
• All spontaneous process results in an increase in Entropy.
• Every system which is left to itself will on the average change towards a condition of
maximum probability. This is captured by Entropy
S = k lnΩ k = Boltzmann Constant
Ω = no. of different ways in which energy of a system can be achieved by arranging the
atoms or molecules among their available states
ENTROPY

• How is the total internal (molecular) energy of a system distributed amongst constituents?
• Eg:Toss 4 unbiased coins
• Similar to the no. of outcome,the total no. of molecular arrangements corresponding to a
macroscopic state is Ω, multiplicity.
• Heat represents the least available form of energy and the transformation of other forms into
heat represents degradation of energy.
• Entropy is the thermodynamic property which serves as a measure of the unavailability or
degradation of energy.
• Higher the degradation of energy – Higher the entropy.
THIRD LAW OF THERMODYNAMICS

•States that the absolute entropy is zero

of a perfectly crystalline substance at
absolute zero of temperature.
REFERENCE PROPERTIES

• Primary properties – used to define the state of the system

• Has absolute Values
• Pressure,P
• Temperature, T
• Volume,V
• Entropy, S
ENERGY PROPERTIES

• Also known as thermodynamic potentials

• Extensive thermodynamic properties
• Can be measured relative to some reference state
• Changes in these thermodynamic functions indicate useful
work hence called energy properties
• U,H,A,G
ENERGY PROPERTIES IN TERMS OF BOUNDARIES

• Internal Energy, U = U(S,V,N) dU = TdS-PdV+μdN

• Enthalpy, H = H(S,P,N) dH = TdS+VdP+μdN
• Helmholtz Free energy, A = A(T,V,N) dA = -SdT-PdV+μdN
• Gibbs Free Energy, G = G(T,P,N) dG = -SdT+VdP+μdN
* Free Energy
 ENERGY CHANGES IN LIVING SYSTEMS

• Biochemical Reactions, Metabolism and Cellular activities

• Enthalpy – internal energy of the system + energy required to displace its surroundings to
make room for the system
• ∆H(Change in enthalpy) – Energy absorbed or released during a reaction
• ∆H is +ve → endothermic reac on
• ∆H is -ve → exothermic reac on
• Entropy – unavailability of energy to do useful work
• ∆S is +ve → more disorder, spontaneous
• ∆S is -ve → more order
 ENERGY CHANGES IN LIVING SYSTEMS

• Free Energy, G – energy that is available in the system to do work at constant T

and P
• ΔG is negative (ΔG < 0), the process is spontaneous (exergonic), meaning it
can occur naturally without additional energy input.
• If ΔG is positive (ΔG > 0), the process is non-spontaneous (endergonic),
meaning it requires energy to proceed.
• If ΔG is zero (ΔG = 0), the system is at equilibrium, and no net change
occurs.
FREE ENERGY, ENTHALPY, ENTROPY AND THEIR
RELATIONSHIP
• ΔG = ΔH – TΔS T – absolute temperature
• How This Applies to Living Systems:

 Catabolic reactions (such as the breakdown of glucose in cellular respiration) tend to be

exergonic and release energy, which can then be used by the cell to perform work.

 Anabolic reactions (such as protein synthesis) are often endergonic and require energy
input, which typically comes from ATP hydrolysis (the breakdown of ATP, a molecule rich in free
energy).

• By coupling exergonic reactions (which release energy) to endergonic reactions (which require
energy), cells can maintain their functions and life processes.
FREE ENERGY CHANGES IN BIOCHEMICAL REACTIONS –
HYDROLYSIS OF ATP AND OTHER HIGH ENERGY
PHOSPHATE COMPOUNDS
ATP Hydrolysis: ATP is often referred to as the "energy currency" of the cell because it stores and provides energy
for a variety of cellular processes. When ATP is hydrolyzed (broken down by water), it releases energy that can be
harnessed by the cell for work.

• The hydrolysis of ATP occurs in two steps:

• ATP + H₂O → ADP + Pi (Inorganic phosphate) + Energy, ΔG = -30.5kJ/mol (pH 7, 1 M

concentration of reactants)

• ATP + H₂O → AMP + PPi (Pyrophosphate) + Energy (less common, but occurs in certain reactions) –
higher energy as it involves the breaking of two high energy bonds. ΔG = -45.6kJ/mol

• The free energy change for the hydrolysis of ATP is negative, making the reaction exergonic (releases energy).
FREE ENERGY CHANGES IN BIOCHEMICAL REACTIONS
SUCH AS HYDROLYSIS OF ATP AND OTHER HIGH
ENERGY PHOSPHATE COMPOUNDS
High-Energy Phosphate Compounds - ATP is not the only high-energy phosphate compound in biological systems. Other compounds
such as phosphoenolpyruvate (PEP), creatine phosphate, and GTP (guanosine triphosphate) also play key roles in energy transfer and
storage.

 Phosphoenolpyruvate (PEP): This molecule has a high-energy phosphate bond and can transfer a phosphate group to ADP to
form ATP in reactions like glycolysis. The ΔG for PEP hydrolysis is approximately -61.9 kJ/mol (or -14.8 kcal/mol), which is
greater than that for ATP hydrolysis.

 Creatine Phosphate (CP): In muscle cells, creatine phosphate serves as a reserve energy source for the rapid regeneration of
ATP during muscle contraction. The free energy change for the hydrolysis of creatine phosphate is around -43.1 kJ/mol (or -10.3
kcal/mol).

 GTP: Similar to ATP, GTP can be hydrolyzed to GDP (guanosine diphosphate) and inorganic phosphate, releasing energy that is
used in processes like protein synthesis, signal transduction, and cellular division.The free energy change for GTP hydrolysis is
roughly similar to that of ATP hydrolysis.
FREE ENERGY CHANGES IN BIOCHEMICAL REACTIONS
SUCH AS HYDROLYSIS OF ATP AND OTHER HIGH ENERGY
PHOSPHATE COMPOUNDS
• Coupling Reactions: Energy released from the exergonic reactions can be used to drive the
endergonic reactions

• Example of ATP Coupling: In the synthesis of macromolecules (like proteins, nucleic acids, and
polysaccharides), ATP hydrolysis provides the energy necessary for the formation of covalent bonds
between monomers (e.g., linking amino acids in protein synthesis).

• Example of Ion Pumps: The Na+/K+ ATPase pump uses ATP hydrolysis to transport sodium
and potassium ions across the cell membrane, creating a gradient essential for nerve impulse
transmission and other cellular functions.
CALORIMETRY

Basic Principles of Calorimetry:

• Calorimetry involves the measurement of heat exchange during a reaction or

process(metabolic processes). The basic principle is that heat is either absorbed or released by
a system during a physical change, chemical reaction, or biological process, and calorimetry
helps quantify this change
• In biological contexts, calorimetry can be applied to measure the heat released or absorbed
during reactions like:
• Respiration (the breakdown of food molecules for energy), Digestion, Metabolic
processes, Muscle activity, Heat production by organisms (e.g., thermoregulation in
animals)
 TYPES OF CALORIMETERS

 Differential Scanning Calorimetry (DSC)

 Bomb Calorimeter
 Respirometry (Indirect Calorimetry)
APPLICATIONS TO BIOLOGICAL SYSTEMS

• Measuring Heat from Cellular Respiration

• Measuring Metabolic Rate

• Energy Expenditure in Exercise

• Thermogenesis and Heat Production

APPLICATIONS IN UNDERSTANDING ENERGY
FLOW
• Energy Yield from Different Substrates

• Dietary Studies and Food Metabolism

EFFECT PH AND CONCENTRATION ON NET FREE
ENERGY CHANGES
• Effect of pH on Free Energy Change: For reactions involving proton (H⁺) transfer or reactions that
are sensitive to the concentration of hydrogen ions (H⁺). This is because the concentration of
hydrogen ions affects the equilibrium position of a reaction, which, in turn, impacts the free energy.
[Products]
ΔG= -RTlnQ Q
[Reactants]
• If Q > 1 - reaction will tend to proceed towards the products, ΔG will be negative, making the
reaction spontaneous.

• If Q < 1: reaction will tend to proceed towards the reactants, ΔG will be positive, making the
reaction non-spontaneous.

• If Q = 1 (equilibrium): The system is at equilibrium, and ΔG = 0

EFFECT PH AND CONCENTRATION ON NET FREE
ENERGY CHANGES

Effect of pH and Concentration Together:

• Enzyme Activity
• Metabolism – Glycolysis (glucose to pyruvate)
QUESTIONS

• Limitation of 2nd law

• Qualitative difference between heat and work
• Diff between standard and Active free energy change
• Characteristics of high energy biomolecules
• High Chemical Bond Energy
• Easy Hydrolysis
• instant Availability
• relatively Stable in Storage
• Energy Transfer