THE FIRST LAW OF

 THERMODYNAMICS
The first law of thermodynamics is known
as the conservation of energy principle.
 It states that energy can be neither created
nor destroyed; it can only change forms.

Energy
cannot be
created
or
destroyed
; it can The increase in the energy of a
only potato in an oven is equal to
change the amount of heat
forms. transferred to it.
 THE FIRST LAW OF
 THERMODYNAMICS
For all adiabatic processes between two
specified states of a closed system, the net
work done is the same regardless of the nature
of the closed system and the details of the
process.

The work (electrical) done on an The work (shaft) done on an

adiabatic system is equal to the adiabatic system is equal to the
increase in the energy of the increase in the energy of the
system. system.
 THE FIRST LAW OF
 THERMODYNAMICS
It provides a sound basis for studying the
relationships among the various forms of energy and
energy interactions.

 The net change (increase or decrease) in the total

energy of the system during a process is equal to
the difference between the total energy entering and
the total energy leaving the system during that
process.
Total energy   Total energy   The change in 
    
 entering the system   leaving the system   energy of the system 
total
 Change in total energy of the system is compensated
by an equal and opposite change in the total energy
of the surrounding
 Energy Balance for Closed
Systems
A closed system moving relative to a reference
plane is shown below where z is the elevation of
the center of mass above the reference plane and
u is the velocity
of the center of mass

Close u
Heat d
Syste Wor
m z k

Reference Plane, z = 0
 Energy Balance for Closed
Systems
 Total energy

  Total energy   The change in 
 entering the system   leaving the system   energy of the system 
total
o Ein  Eout  Esystem
r
Consider the energy added to be net heat transfer and the energy
leaving the closed system to be net work done by the closed
system.
Qnet  Wnet 
Esystem
The total energy of the system, Esystem, is given as
E= Internal energy + Kinetic Energy + Potential Energy
E= U+ PE+ KE

🢥 ΔU+ ΔPE+ ΔKE = Q -W

 Energy Balance for Closed
Systems

In many applications of first law , the system

undergoes no change in external potential or
kinetic energy, but only changes in internal
energy. For the Non-flow process, First Law
becomes

ΔU = Q - W
[Example]A system consistingof some fluid is stirred in
a tank. The rate of work done on the system by the
2.25
stirrerhp.
is The heat generated due to stirring is dissipated
to the surroundings. If the heat transferred to the
surroundings is 3400 kJ/hr, determine the change in
internal energy.

Work done on system = -

2025 hp 1 hp = 0.7457 KW
W = -2025(0.7457) = -1510.
0425 KW

Heat transferred to surrounding =Q = -3400 KJ/h = -0.

9444 KW Doing energy balance for closed system
U=Q-W
U = -0. 9444 - (-
1510.0425) U =
1509.0981 KW
U = 1509.0981 KW =
5432753.16 KJ/h
[Example] A tank containing a fluid is stirred by a
paddle driven by a 2 hp motor. Heat losses from the
tank are 378 kcal/hr. Does the internal energy of the
system which is 10 kg of the fluid in the tank increase
or decrease? Determine the change in specific
internal energy
[Example] A car riding downhill at a speed of 20 m/s was
applied brake when it was at height of 30 m vertically above the
bottom of a hill. When the car comes to a halt at the bottom
of the hill, how much energy as heat must be dissipated by
the brakes, if the wind and other frictional effects are
neglected? The car weighed 1400 kg.
[Example] Water flows over a waterfall 100 m height.
Take 1 kg of the water as the system, and assume that
it does not exchange energy with the surroundings.
(i) What is the potential energy of the water at the
top of the of the falls with respect to the base of
the falls?
(ii) What is the kinetic energy of the water just before
it
strikes bottom?
(iii) After the 1 kg of water enters the river below the
falls, what change has occurred in its state?
[Example] When a system is taken from state a to state b in
Fig. 1 along path acb, 100 J of heat flows into the system
and the system does 40 J of work.
(i) How much heat flows into the system along path aeb if
the work done by the system is 20 J?
(ii) The system returns from b to a through bda. If the work
done on the system is 30 J, does the system absorb or
liberate heat? How much?
ΔU=80−30=50
ΔU is state function
(a) ΔU=q+W
50=q−10
orq=60J
(b) ΔU=−50
ΔU=q+w
q=ΔU−w=−70
(c) ΔUABD=ΔUAD+ΔUDB
50=40+ΔUDB
ΔUDB=10
ΔUDB=q+w
10=q+0[Vol. const.]
q=10J
Total work in WADB=−10
WAD+WDB=−10
WAD=−10
ΔUAD=q+w
40=q−10
q=50
[Example] A system consisting of a gas confined in a
cylinder is undergoing the following series of processes
before it is brought back to the initial conditions:
Step 1: A constant pressure process when it receives 50 J
of work and gives up 25 J of heat.
Step 2: A constant volume process when it receives 75 J of
heat. Step 3: Adiabatic process.
Determine the change in internal energy during each
step and the work done during the adiabatic process.
 ΔU1 = 50J - 25J

ΔU1 = + 25J

Step 2

at constant volume(i.e. work is zero) it receives(+) 75J

Heat

ΔU2 = 0 + 75J

ΔU2 = +75J

Step3

adiabatic process (i.e. Q=0) work is done

ΔU3 = Q + W

ΔU3 = W (Q=0)

as this is a cyclic process ΔUtotal must be zero

ΔUtotal = ΔU1 + ΔU2 + ΔU3 = 0

 Ideal gas
 An ideal gas as one in which the distance
between the molecules is so large that the inter-
molecular forces are negligible and the volume
occupied by the molecules is only a negligible
fraction of the total volume.
 It follows from kinetic theory that for such a
fluid the product of pressure and volume
varies linearly with temperature.
 This is stated mathematically by the ideal gas
equation PV = RT
where R is a constant known as the ideal gas
constant and V is the molar volume of the gas.
 All real gases behave ideally as pressure is
reduced to zero.
[Example]Iron filings are
contained in
cylinder an atmosphere aof oxygen. It
combines with oxygen according to the
in
following reaction.
2 Fe + (3/2) O2  Fe2O3
The pressure inside the cylinder is
maintained at 101 kPa. The temperature is
kept constant at 298 K by removing heat.
For 2 mol iron reacted, calculate W and ΔU
given that 831.08 kJ of heat is liberated in
the process.
 Reversible process
 In a reversible process, the driving and opposing
forces are in exact balance, and an infinitesimal
change in the external conditions would cause a
reversal in the direction of the process.
 For reversible process to occur, friction , turbulence
and
other dissipative effects should be absent.
 It takes an infinite time for its completion.
A reversible process occurring in a work-producing
machine delivers the maximum amount of work and
that in a work- requiring machine requires the
minimum amount of work.
A reversible process is an idealised and imaginary
concept and may be used for the comparison of the 1
5
performance of actual systems and for indicating the
[Example] 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
surrounding. Will it be the same as the work
done by the gas?
kg/kmol.

So, 2 kg CO2 = 2 kg * 1kmol/44 kg = 1/22 kmol

of CO2 = n, number of moles in the system.

Initial system pressure, Pi = 6.5 bar = 6.5 bar *

100 kPa/1bar = 650 kPa.

Initial temperature of system = Ti = 300K.

By ideal gas law, P.V = nRT, where R = 8.314

kPa.m3/kmol.K

so, initial volume = Vi = n.R.Ti/Pi = 1/22 * 8.314

* 300 / 650 = 0.1744 m3.

Final volume after expansion = Vf = 2*Vi.

Now, work done by a gas system on the

surrounding = surrounding pressure * (final
volume - initial volume).

Surrounding pressure = atmospheric pressure +

pressure applied by piston.
pressure by piston = mass of piston * gravity /
surface area = 5000 kg* 9.81 m/sec2 / 1m2 =
49050 Pa = 49.05 kPa.

Surrounding pressure, Ps = 101.325 + 49.05 =

150.375 kPa.

So, work done by gas on the surrounding = Ps *

(Vf - Vi) = Ps*(2Vi - Vi) = 150.375 kPa * 0.1744
m3 = 26.2254 kJ.

= the work appearing in the surrounding.

Gas has to done some work to overcome the

frictional resistance. So, total work done by the
gas = work done on the surrouonding + work
done to overcome friction.
[Example] A gas which occupies a volume of 0.2 m3 at a
pressure of 1 bar is expanded to a final pressure of 7 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.
Therefore; the pressure volume relation
becomes:

P = 1200 V - 140

Pressure after expansion = 7 bar = 700 kPa

Now; we calculate the volume after expansion.

700 = 1200 V - 140

1200 V = 840

V = 840 / 1200 = 0.7 m3

The work done by the gas is given by:

\tiny W =\int_{V_{1}}^{V_{2}}P.dV

substituting the value of P in the above integral

we get:

\tiny W =\int_{V_{1}}^{V_{2}}(1200V-140).dV

which on integration gives:

Internal Energy and
Enthalpy  In the analysis of
systems that
involve fluid flow,
we frequently
encounter the
combination of
properties U and
PV.
 The combination is
defined as enthalpy (H
= U + PV).
 The term PV
represents the flow 1
energy of the fluid 8
 Enthalpy
 Sinceinternal energy (U), absolute pressure (P)
and volume of the system (V) are state
function, any combination of them including,
Enthalpy are state function.
 Theproduct, PV, represents the work that must
have been done against an environmental
pressure (P) to create a volume (V) occupied by
the system. (The Energy that the system
possesses because of it occupying a space.)

𝐻 = 𝑈 + 𝑃𝑉 🢥 𝑑𝐻 = 𝑑𝑈 +
𝑑(𝑃𝑉) ∆𝐻 = ∆𝑈 +
∆(𝑃𝑉)
🢥
 Constant-V and constant-P
 The general 1st law equation for a
mechanically reversible, closed-system
process:
dU  dQ  PdV
• constant total volume:
- Q  U
– the heat transferred is equal to the internal-energy
• constant dQ  dU  d (PV ) dQ  d (U  PV
change of the system
pressure: )
- Q  H
– the mathematical definition of HU
enthalphy: PV change of
– the heat transferred is equal to the enthalpy
the
system
[Example] Calculate ΔU and ΔH in J for 1 kmol water, as it is
vapourized at the constant temperature of 373 K and
constant pressure of 101.3 kPa. The specific volume of the
liquid and vapour at these conditions are 1.04 × 10-3 and
1.675 × 10-3 m3/kmol respectively; 1030 J of heat is added
to water for this change.
[Example] Liquid CO2 at 233 K has a vapour pressure of
1.005×103 kPa and a specific volume of 0.9 ×10–3 m3/kg.
Assume that CO2 is a saturated liquid at these conditions and
its enthalpy is zero. Latent heat of vaporization of CO2 is 320.5
kJ/kg and the specific volume of saturated vapour is 38.2×10–3
m3/kg. Calculate the internal energy of saturated liquid, and
internal energy and enthalpy of saturated vapour.
 Electrical Work
 The rate of electrical work done by electrons
crossing a system boundary is called electrical
power and is given by the product of the voltage
drop in volts and the current in amps.
We  V I (W)
 The amount of electrical work done in a time
period is found by integrating the rate of
electrical work over the time period.

2
We V I dt
1
(kJ)

[Example] An electric current of 0.5 A from a 12 V supply is
passed for 5 minutes through a resistance in thermal contact
with saturated water at 1 atm. As a result, 0.798 g of water is
vapourized. Assuming that the water vapour behaves ideally,
calculate the molar internal energy change and enthalpy
change during this process.
[Example] A piston–cylinder device contains 0.1 kg of
saturated water vapour that is maintained at a constant
pressure of 400 kPa. Heat is supplied by means of a
resistance heater provided within the cylinder. A current of
0.2 A from a 230-V source is passed continuously for 10
min. Heat loss from the system is estimated to be 15.41 kJ.
Making use of steam tables, determine the final
temperature of the steam.
First law of thermodynamics for
Open Systems / Control
Volume

2
6
Mass balance for open
systems:
Total mass   Total mass    The change in 
 entering the system   leaving the system   mass of the
total 
system 
m
1  2  dmcv
m dt
dmcv
(m ) 2  1 🢥  (m ) (uA)
m  m dt
Where,
m  m=
m t mass t
= time
• Energy balance for open
systems
 Total energy

  Total energy    The change in 
 entering the system   leaving the systemtotal
  energy of the system 

Ein  Eout  Esystem

The energy added Q and the energy leaving Ws (shaft work)
by the
open system.
Q − 𝑊𝑠 = ∆𝐸 𝑠𝑦𝑠𝑡𝑒𝑚

The total energy of the system, Esystem, is given as

E= InternalE=
energy ++
U + PV 🢥 +
Flow energy E=Kinetic
H + PE+Energy +
Potential Energy
PE+ KE KE
🢥 ΔH + ΔPE+ ΔKE = Q -
Ws
Energy balance for open systems in terms of
specific

𝑚ሶ ∆𝐻 + ∆𝑃𝐸 +∆𝐾𝐸
properties

= 𝑄 − 𝑊𝑠
Where
H , PE and KE are specific

𝑚ሶ
properties
is mass flow rate
Q is rate of heat input
Ws is rate of work
done
[Example] A steam turbine using steam at 1368 kPa and 645 K
and discharging saturated steam at 137 kPa is used to
generate power for certain chemical plant. The turbine acts
adiabatically and the feed and discharge velocities may be
considered equal. Determine the theoretical horsepower
developed by the turbine if it uses 1650 kg steam per hour.
From the steam tables, enthalpy of superheated steam at 1368
kPa and 645 K is 3200 kJ/kg and enthalpy of saturated steam
at 137 kPa is 2690 kJ/kg.
[Example] A liquid mixture containing 50 mol percent each of
benzene and toluene at 313 K is to be continuously flash
vaporised so that 60 mol percent of the feed is vaporised. The
residual liquid product contains 35 mol percent benzene. If the
enthalpies per mole of feed, distillate and the residue are
respectively 5, 30 and 2 kJ/mol, calculate the heat added in kJ
per mole of vapour product.
[Example] Steam at 1800 kPa and 673.15 K steadily enters a
nozzle at a rate of 5 kg/s and leaves the nozzle at 1400 kPa
with a velocity of 300 m/s. The inlet area of the nozzle is 0.02
m2. Heat losses from the nozzle per unit mass of the steam
are estimated to be 3.3 kJ/kg. Determine the exit temperature
of the steam.
[Example] Water is flowing in a straight horizontal insulated
pipe of 25 mm i.d. There is no device present for adding or
removing energy as work. The upstream velocity is 10 m/s.
The water flows in a section where the diameter is suddenly
increased. What is the change in enthalpy if the downstream
diameter is 50 mm?
 HEAT CAPACITY
 The heat capacity (C) of a substance is the quantity of
heat to be supplied to effect a temperature rise of one
degree. dQ
C
dT
– a process-dependent quantity rather than a state
function.

 Heat capacity of unit mass of a

substance is also known as specific
heat of the substance.
– The specific heats of a substance, in
general, depend on two independent
properties such as temperature and
pressure.
– At low pressures all real gases approach
ideal gas behavior, and therefore their
specific heats depend on temperature
 HEAT CAPACITY
 Two kinds of specific heats:
– specific heat at constant volume cV
– specific heat at constant pressure cP

 CV and CP, are in common use for

homogeneous fluids; both as state
functions, defined unambiguously in
relation to other state functions.
 HEAT CAPACITY
• At constant • At constant
volume
Q pressure
Q
𝜕 𝜕
U H
𝐶𝑉 𝑄 𝐶𝑃 𝑄
𝜕 𝜕
= 𝑇 = �
𝑇
�
� �
CV   U  C P   H 
   
T  V T  P
T2 T2
V (const P (const P)
U  C
T1 dT V) H  C
T1 dT
[Example] Water at 368 K is pumped from a storage tank at
the rate of 25 m3/hr. The motor for the pump supplies work at
the rate of 2 hp. The water passes through a heat exchanger,
where it gives up heat at the rate of 42000 kJ/min and is
delivered to a second storage tank at an elevation of 20 m
above the first tank. What is the temperature of the water
delivered to the second storage tank? Assume that the
enthalpy of water is zero at 273 K and the specific heat of
water is constant at 4.2 kJ/kg K.
[Example] Heat is transferred to 10 kg of air which is initially
at 100 kPa and 300 K until its temperature reaches 600 K.
Determine the change in internal energy, the change in
enthalpy, the heat supplied and the work done in the
following processes:
(a) Constant volume process.
(b) Constant pressure process.
Assume that air is an ideal gas for which the P-V-T relationship is
PV =
nRT. Take CP =29.099 kJ/kmol K and CV =20.785 kJ/kmol K.
[Example] The P-V-T behaviour of nitrogen is represented
by the ideal gas equation PV = nRT. Where n is the number
of moles of the gas and R is the ideal gas constant. The
heat capacity of the gas are CP =29.1 kJ/kmol K and CV
=20.8 kJ/kmol K. The gas initially at 10 bar and 280 K is
undergoing a change of state to the final condition of 1 bar
and 340 K. Determine the change in internal energy and
change in enthalpy.
[Example] Hydrogenation of an oil is carried out in a reactor at
a pressure of 136.8 kPa and a temperature of 453 K. The
hydrogen gas at 293 K is heated to 453 K by passing through a
coil where it experiences a pressure drop of 300 kPa. Hydrogen
behaves like an ideal gas and its heat capacity at constant
pressure is 29.4 kJ/kmol. Neglecting kinetic energy effects
determine the heat transfer rate in the coils per 1000 kg
hydrogen.