FIRST LAW OF

THERMODYNAMICS
Notes Set 2
 THE FIRST LAW OF
THERMODYNAMICS
This law correlates with the law of conservation of energy.
The law of conservation of energy of energy states that; Energy can
neither be created nor destroyed but can be changed from one form
to another.

The first law of thermodynamics is portraits the general principle of

conservation of energy but with reference to thermal energy i.e. heat
and mechanical energy i.e. work

When a system undergoes thermodynamic cycle the intrinsic energy of

the system at the beginning and at the end is the same.
And since the intrinsic energy is unchanged, the first law thermodynamics states
that;
When a system undergoes a thermodynamic cycle, the net heat supplied to the
system from the its surroundings plus the network input to the system from its
surroundings must be equal to zero.
Applications of first law of thermodynamics
 heat engines
 Power generation
 Refrigeration and air conditioning
 Biological systems
 Aerospace engineering
 Food processing
 Building insulation and energy efficiency
 Medical equipment
Example
In a certain steam plant the turbine develops 1000kw.
The heat supplied to the steam in the boiler is
2800J/kg, the heat rejected by the steam to the cooling
condenser is 2100J/kg and the feed pump work
required to pump the condensate back into the boiler
is 5kw. Calculate the steam flow rate.
 LIMITATIONS OF FIRST LAW OF THERMODYNAMICS
• Does not account for energy conversion efficiency; the 1st law of
thermodynamics only states that energy is conserved but does not
specify how much energy is converted from one form to another
• Ignores entropy and disorder; the 1st law doesn’t consider the
increase in entropy that accompanies energy transfer.
• Assumes a closed system; The 1st law applies to closed systems where
no matter or energy is exchanged with the surrounding.
• Assumes a uniform temperature; The 1st law assumes a uniform
temperature throughout the system which is not always the case.
• Does not predict direction of spontaneous process; the first law
doesn’t indicate weather the process will occur spontaneously or not
 State functions and Path functions
• State function; Is a property • Path function; Is a property
whose value does not depend on whose depends on the path
the path taken to reach that taken to reach a specific value.
specific value Examples
Examples Work
Internal energy Heat

Entropy
Enthalpy
Gibbs Free energy
Helmholtz Free energy
 INTERNAL ENERGY
• This is the sum of energies in a given system.
• In experiments like the joule’s experiment, the energy transferred to the fluid as
work was later transferred from it as heat.
• Hence the energy was contained in the fluid as internal energy.
• INTERNAL ENERGY OF A CLOSED SYSYEM
Internal Energy Of A Closed System
• Consider an ideal gas heated in a cylindrical closed system with a piston.
• The heat supplied increases the kinetic energy of the molecules of the gas,
• Since the internal, energy of an ideal gas is equal to the change in kinetic energy.
The internal energy of the system increases.
• Since change kinetic energy of the molecules is proportional to the temperature
change
• It therefore implies that change internal energy is proportional to the change in
temperature.
• The internal energy of a system refers to the overall energy present
within the system, excluding the kinetic energy associated with the
system's collective motion and the potential energy associated with
the system as a whole.

The internal energy of a system can be augmented through the

addition of matter, the transfer of heat, or the performance of work
on the system.

U=∑iEi
Note
 Internal energy can not be measured absolutely but instead we
determine the change in internal energy of the system.

 Internal energy deals with energy of the molecules in a system.

 For a fluid system, heated at constant volume, the heat supplied is

equal to the internal energy.

 When heat is supplied to the system ∆Q is positive (Endothermic).

 When heat is lost by the system ∆Q is negative (Exothermic).

 When work is done on the system ∆W is negative.

 When work is done by the system ∆W is positive.

Examples

Qn1) A system received a continuous supply of 600 joules of heat at constant volume. The system's
temperature rose from 30 to 35 degrees Celsius as a result. In what ways has the system's internal energy
changed?
Qn 2) Which energy is not the part of the internal energy?
a) Nuclear Energy
b) Chemical bond energy
c) Gravitational Energy
d) Potential Energy
Qn 3) ΔU is zero in
a) Isobaric process
b) Cyclic process
c) Adiabatic process
d) Isochoric process

Qn 4) The molar enthalpy change for the condensation of 1 mol of water at 1 bar and 100 °C is 51kJ/mol if
water vapor is taken to be a perfect gas. Determine the internal energy when 1 mol of water condenses at 100
°C and 1 bar of pressure.

Qn 5) Why is it preferable to determine the change in enthalpy than change in internal energy?
ENTHALPY
• Is the amount of heat in a system.
• Is the amount of heat absorbed or released by a system to cause
change in a system.

Enthalpy is denoted as;

H = U + PV
OR: ∆H=∆U+P∆V
Where P is pressure
V is volume
U is internal energy
 RELATIONSHIP BETWEEN ENTHALPY AND FIRST
LAW OF THERMODYNAMICS

AT CONSTANT PRESSURE AT CONSTANT VOLUME;

∆H=∆U + P∆V…………………(Eqn1) ∆H= ∆U + P∆V, but P∆V=0 since there is
no work done; ∆H= ∆U...(Eqn1)
From the first law of thermodynamics;
Q= ∆U + P∆V; P∆V=0
Q=∆U + P∆V; ∆U=Q-P∆V………….(Eqn2)
Implying, ∆H= ∆U= Q
Substitute Eqn2 in Eqn1
Therefore; ∆H= Q ( for constant
∆H=Q - P∆V + P∆V volume)
∆H=Q (For constant pressure)
Note;
• The absolute value of enthalpy can NEVER be found
but rather the change in enthalpy (∆H) i.e. E=
impossible
• ∆H for a cyclic process is always 0 because final
enthalpy and initial enthalpy are the same
• ∆H is a state function i.e. depends on the final and initial
value but is independent of the path taken
• ∆H is extensive i.e. depends on the amount of
substance, the smaller the amount of substance the
smaller the enthalpy and vice versa.
Example
Qn 1) One mole of an ideal gas undergoes from (3atm, 5l,
80k)to (6atm, 7l, 200k) with a change in internal energy
of 50l-atm. Find the change in enthalpy

Qn 2) Calculate the change in enthalpy and internal

energy for 1kg of water when it is vaporized at a constant
temp of 100˚C and constant pressure of 101.33Kpa.The
specific volumes of water and vapour at these conditions
are 0.00104 and 1.673m3kg-1, respectively. For this
change, heat in the amount of 2256.9KJ is added to
water.
 STEADY FLOW PROCESSES
• Steady flow refers to the condition where the fluid properties at a
point in the system do not change over time.
• Steady state flow is the one in which fluid properties e.g. velocity,
pressure at any given time remain constant over time.
EXAMPLES OF STEADY STATE FLOW.
• Heating one end of a steel rod, the whole rod gets heated after a
certain time.
• Filling a bucket of water with open tap, given that poured water is
equal to the discharged water, the level of water remains constant.
STEADY FLOW DEVICE
This is a device that experiences a constant flow of materials through it. Like
pumps, nozzles, diffusers, compressors, turbines.
PRINCIPLE OF STEADY STATE FLOW.
It states that the properties of a fluid remains constant at a given point over time
provided there is no change in the energy or mass of the system.
Types Of Steady State Flow
Laminar
Quasi flow

LAMINAR FLOW
Is the type of flow that occurs when the fluid particles follow smooth paths in
layers. It is also called streamlined flow.
QUASI STEADY STATE FLOW;
This is the flow where the vortices are created behind an object that is in uniform
flow. And it is considered to be transient flow
CONDITIONS FOR STEADY STATE FLOW
The fluid flow is steady, hence the properties are constant.
The fluid is incompressible.
The fluid is Newtonian: the viscosity doesn’t change with time or density
The fluid flow is adiabatic: there is no heat transfer between the fluid and the
surrounding
The fluid is isothermal: temperature remains constant through the flow.

APPLICATIONS OF STEADY FLOW

In the fields of economics, electronics, electrical and mechanical engines, fiber optics
and pharmacy.
The flow of water through a pipe, extraction of oil from vertical well, operation of
turbines on aero plane.
It is applied to the engineering devices that undergo thermodynamic processes e.g.
boilers, nozzles, diffuses, mixing chambers, heat exchange of turbines.
EQUILIBRIUM IN THERMODYNAMICS
• Equilibrium in thermodynamics is a fundamental concept that
describes a state where there are no net macroscopic flows of matter
or energy within a system or between systems
OR Equilibrium refers to a state where a system's macroscopic
properties (such as temperature, pressure, and volume) remain
constant over time.
OR Equilibrium refers to a state in which a system is in a stable balance
with its surroundings, with no net change in any of its properties over
time.
Conditions For Equilibrium
• For a system to be in thermodynamic equilibrium, all intensive properties
(such as temperature and pressure) and extensive properties (such as
internal energy and entropy) must be constant throughout the system.
• The system must have uniform temperature, pressure, and chemical
potential for all species.
Note:
Intensive properties are physical and chemical properties that do not depend
on the size or quantity of a substance. They remain constant regardless of the
amount of the system. E.g. Temperature, Pressure, Density, Specific heat
Capacity, Chemical potential.
Extensive properties are physical and chemical properties that depend on the
size or extent of the system E.g. mass, volume, Internal Energy, Enthalpy,
Entropy.
Characteristics Of Equilibrium
• Uniformity of Properties
• Stability
• Predictability
• Absence of Macroscopic Flows
• Maximization of Entropy
• Minimization of Thermodynamic Potentials
• Balance of Driving Forces
TYPES OF EQUILIBRIUM
1. Thermal Equilibrium: This occurs when two or more systems in contact
with each other reach the same temperature and no heat flows between
them. Essentially, their temperatures become equal, and there's no net
energy transfer due to temperature differences.
NOTE: Zeroth's law states that "If two systems are each in thermal
equilibrium with a third system, then they are in thermal equilibrium with
each other.“
2. Mechanical Equilibrium: This is achieved when there are no net forces
acting within the system, meaning that the pressure is uniform throughout
the system, and there is no net movement of the system's parts. In a closed
system, this implies that the pressure is the same in all parts of the system.
Systems have the same pressure, indicating no bulk movement of fluids.
3. Chemical Equilibrium: This is when the rates of the forward and reverse chemical reactions are
equal, so that concentrations of reactants and products remain constant over time.
The chemical potentials of all species are the same in all phases, indicating no net transfer of species.
An illustration of chemical equilibrium is the industrial process called the Haber process (manufacture
of ammonia)

Factors Affecting Chemical Equilibrium

• Pressure
• Concentration
Increase in reactant concentration increases reaction rate and shifts equilibrium sign to the right.
• Temperature
Increase in temperature favors endothermic reactions (forward reactions)
• Adding a noble gas
• Adding a catalyst
Speeds up forward and reverse reactions by lowering the activation energy hence increasing reaction
rate.
 PHASE EQUILIBRIUM
• This occurs when multiple phases (like solid, liquid, and gas) of a
substance coexist without any net change in the amounts of each
phase. For example, in the case of water at its boiling point, liquid
water and water vapor are in phase equilibrium
PHASE:
Is a homogenous part of a system which is physically distinct from other
parts of the system by a definite boundary.
PHASE DIAGRAM: Is a graph on which pressure is plotted
against temperature showing equilibria between different
phases of a substance and the temperatures and
pressures at which each phase exists.

TRIPLE POINT: Is the temperature and pressure under

which three phases can coexist in equilibrium.
 SINGLE COMPONENT SYSTEMS
Here only one pure chemical substance is involved in the equilibrium.

Examples of one component systems include:

• The water system
• The Sulphur system
• The carbon dioxide system
 THE WATER SYSTEM
• Water can exist as liquid as a
solid or as vapour.
• It is called steam when its
temperature is above 100oc.
Question
• What are the effects of
temperature and pressure on
the phase shown?
 EQUILIBRIUM LAW (LAW OF MASS
ACTION)
• It states that “ if a reversible reaction is allowed to reach equilibrium
at a particular temperature, the product of the molar concentrations
of the products raised to appropriate powers divided by the product
of the molar concentrations of the reactants to appropriate powers is
a constant
NOTE:
Equilibrium constant is the ratio of molar concentration of
products raised to their appropriate powers to the
product of molar concentration of reactants raised to
their appropriate powers in a stoichiometric equation of a
reversible reaction at constant temperature
 RULES OF PHASES
• Phase rule is a principle used to determine the number of degrees of
freedom (independent variables) in a thermodynamic system at
equilibrium.
• It is also known as the Gibbs phase rule.
• It is given by; F = 2+C-P
Where: F is the number of degree of freedom.
C is the number of components in the system.
P is the number of phases present in the system i.e. distinct
physical states of matter like solid, liquid and gas.
• This rule helps us to in understanding how changes in conditions like
pressure, temperature or composition affects the system’s
equilibrium,
Example
• For a single phase; pure liquid water where P=1, where C=1
• F=2+C-P
• F=2
• Therefore the number of degrees of freedom is 2.
 REVERSIBLE PROCESS
• A reversible process is a process whose direction can be reversed in
an opposite direction by an infinitesimally change in external
conditions
• Consider a piston cylindrical tube containing one mole of an ideal gas
with initial volume v1
• If the external or atmospheric pressure is greater than the internal
pressure, the molecules that hold the atmospheric pressure exerts
pressure on the piston which causes contraction of the gas. The
volume decreases to v2.
• When the internal pressure increases, it pushes the piston back hence
equilibrium is attained.
From work done=PdV
From derivation = -2.303log[v2/v1]
 Reversible expansion of an ideal gas

• The nature of reversible processes is illustrated by the expansion of

gas in an idealized piston/cylinder arrangement. The apparatus shown
is imagined to exist in an evacuated space. The gas trapped inside the
cylinder is chosen as the system; all else is the surroundings.

• Assuming there is no external pressure, one mole of a gas is trapped

in a vacuum cylinder with a piston

• The internal pressure expands

• No work done in free expansion since the external pressure is zero

Illustration
Example
• A gas which occupies a volume of 0.2m3 at a pressure of 1 bar is
expanded to a final pressure of 7.0 bar. The pressure of the gas varies
according to the relation P = 1200 V + b, where P is in kPa, V is in m3
and b is a constant. Calculate the work done by the gas.
• Two kilograms of CO2 gas is contained in a piston–cylinder assembly at
a pressure of 6.5 bar and a temperature of 300 K. The piston has a mass
of 5000 kg and a surface area of 1 m2 . The friction of the piston on the
walls is significant and cannot be ignored. The atmospheric pressure is
1.01325 bar. The latch holding the piston in position is suddenly
removed and the gas is allowed to expand. The expansion is arrested
when the volume is double the original volume. Determine the work
appearing in the surroundings. Will it be the same as the work done by
the gas?
Reversible chemical reaction
Consider the chemical reaction occurring in a galvanic cell in which the
electrodes made of zinc and platinum are immersed in an aqueous
solution of hydrochloric acid. The following reaction occurs:
Zn + HCl ZnCl2 +H2
• The electrodes are connected through an external circuit to a
potentiometer. The system is in equilibrium when the applied
potential difference is balanced by the e.m.f. produced by the cell. By
increasing or decreasing the potential difference slightly, the reaction
can be carried out in the forward or reverse direction.
Other examples of reversible
process
• Extension of strings.
• Frictionless motion of solids.
• Slow adiabatic expansion or compression of gases.
• Slow isothermal compression or expansion of gases.
 HEAT CAPACITY
• This is the amount of heat required to increase temperature of an
object by 1K.
Therefore dQ = C dT
• Therefore the amount of heat required to rise a unit mass by 1K is
referred to as specific heat capacity
• Where c= where Q is the heat quantity, m is the mass, and is the
temperature change.
• We also have Molar heat capacity which is the heat required to raise
the temperature of one mole of a substance by a one kelvin.
• The ratio of heat capacities
• Where; Cp is the specific heat capacity at constant pressure
Cv is the specific heat capacity at constant volume.
• Heat capacity at • Heat capacity at constant pressure;
Amount of heat required to rise the
constant volume; temperature of a substance by 1K at constant
pressure. dQ = Cp dT.
Amount of heat required Where Cp is heat capacity at constant pressure.

to rise the temperature of ΔQ=CpΔT

But ΔQ= ΔU + W = ΔH (At constant pressure)
a substance by 1K at ΔH =Enthalpy
constant volume. Therefore;

Δ Q = CvdT ΔH= Cp ΔT

• Where Cv is heat
capacity at constant • Work done = P[V2 – V1]

volume • Internal energy = Cv.∆T

Examples 1
Heat is transferred to 10kg of air which is initially at 100kpa and 300K until its
temperature reaches 600K. Determine the change in internal energy (ΔU), the
change in enthalpy, the change in heat supplied(ΔQ), and work done in the
following processes;
(i) . Constant volume process
(ii). Constant pressure process
Assume P-V-T = nRT, where R= 8.314kJ/kmol K.
Take Cp=29.099kJ/mol K, Cv=20.785kJ/kmol K and molecular weight of the air is 29

Example 2

Air at 1bar and 298.15K is compressed to 3bar and 298.15K by cooling at constant
pressure followed by heating at constant volume. Calculate the heat and work
requirements dU and ΔH of the air for each path. Where Cv = 20.785 and Cp =
21.100J/mol K.
Assume also that air remains a gas for which PV/T is a constant. At 298.15 K and
1bar the molar volume of air is 0.02479m3 mol-1