Prof.

Monica Costea - Lecture 4_First Law (1) 23

Chap.3. FIRST LAW OF TERMODINAMICS

First Law (FL) of Thdyn.= particular case of the general
law of energy conservation and transformation, as a
quantitative measure of the movement of matter.
- brings together the fundamental energy forms:
heat – Q, mechanical work – W, internal energy – U, enthalpy – H.
3.1. Mechanical work
= a form of energy transfer
- is not a point function (state property) for the system, but a path
function (process property),which is dependent on the process
path.
OBS: - the infinitely small variation of a point function (state
property) represents an exact differential => notation "d"
Ex: dp, dT, dV
- a state property variation does not depend on the process
path, but only on the initial and final state.
Ex:
! For mechanical work only the notion of "elementary mechanical
work", denoted with "L" is valid which represents an
infinitely small quantity and not the variation of a quantity.
Notation "" designats an inexact differential
3.1.1. Moving boundary work (pressure forces work or process
work)
a) Expression of the moving boundary work
Prof. Monica Costea - Lecture 4_First Law (1) 24

Let's consider a thdyn. system having a deformable border.

Inside there is a gas having a uniform pressure p, while on the
outside a uniform pressure pe acts.
- due to the pressure difference (p>pe), the system expands.
- the mechanical work performed against pe is a scalar property:

pe
pe D
x A
pe
P
=> - general expression
pe of the moving boundary work
pe

Note: p = p – pe => pe = p – p (+ -)

=> δWe = (p – p)dV = pdV - pdV

Reversible deformation process => p → dp
=> pdV → dpdV = infinitely small of higher order, which is
neglected in relation to pdV

It results: δWrev = pdV and moving boundary

work in reversible (quasi-equilibrium) process
OBS: 1) in W1-2 relation the pressure p is the internal pressure in
the system, and not the external pressure;
2) to  movement, finite differences must  !
=> We = pdV – pdV = Wrev – pdV = Wrev –δirr, p = Wirr
It results that the irreversibility due to pressure finite
difference p leads to a lost of W in the sense that:
Prof. Monica Costea - Lecture 4_First Law (1) 25

and

b) Sign of moving boundary work

If dV > 0 => δW > 0: produced W
dV < 0 => δW < 0: consumed W
V = ct => W = 0: isometric process
c) The graphic significance of moving boundary work
Reversible processes => the sequence of intermediate states can
be represented in a chart.
p Clapeyron introduced the mechanical
p1 1 diagram p-V
pdV
p = area (a12ba)
2
p2 = is represented by the area
a b
between the process curve and the
V1 dV V2 V
abscissa axes
OBS: the moving boundary work is associated with expansion
or compression in piston-cylinder device.
Highlighting the negative nature of irreversible process
(which is carried out with finite speed and finite variation of state
parameters):
1) Expansion

At equilibrium in the initial state:

G
pe1 = pa + 1 = p1
Ap
If G1 is suddenly replaced with a
smaller weight G2, the gas suddenly
Prof. Monica Costea - Lecture 4_First Law (1) 26

expands, and the new equilibrium state corresponds to the internal

pressure p2:
G
P pe2 = pa + 2 = p2  p1
pe2=p2 1 Ap
Wlost
γ 12: the process described (irrev.);
1γ2 : small graduated weight
 2
pe1=p1 reductions, reversible process.
a b
= area (a1γ2ba) > area (a2ba)
V1 V2 V
The process was accompanied by V
=> W > 0.
Reversible process => Wmax is produced.
Loss of W in the process of irreversible expansion:
Wlost = Lrev
1− 2
- Lirev
1− 2
= area (121)

2) Compression
G1
pe1 = pa + = p1 at equilibrium
Ap
G2 > G1

G2
pe2 = pa + = p2  p1
Ap

P 2 β
=p2 = area (bβ2ab) < 0
Wadded
= area (b1γ2ab) < 0
γd
pe1=p1 1  < 
a b
V2 V1 V
Prof. Monica Costea - Lecture 4_First Law (1) 27

W for compression is < 0 (consumed) => in reversible processes

the minimum mechanical work is consumed to achieve a useful
effect.
Wadded = – 
Thus, in reversible processes:-> Wmax is produced
-> Wmin is consumed
3.1.2. Flow work
- also called dislocation energy or work
= mechanical work necessary for a fluid into an environment
characterized by a certain pressure.

The mechanical work

necessary to dislocate the gas from
position I to II is:
W=pAx = pV
The mechanical work done on a
quantity of gas occupying the volume V at pressure p and
temperature T, to move it at p = ct, is called dislocation of flow
work and is given by:
W = pV
- it does not increase the energy of the gas in the pipeline;
- it is transmitted throughout the gas mass, leading to an
increase in the energy of the gas accumulated, possibly in a
reservoir R.
OBS: This work admits an exact differential (as opposed to the
moving boundary work) as it characterizes potential energy due to
the pressure of the fluid.
 Prof. Monica Costea - Lecture 4_First Law (1) 28

3.1.3. Shaft work (technical or total mechanical work)

- accompanies the processes in the thermal machines in which

mass exchange with the external environment takes place.
The cylinder of a pneumatic engine connected to the external
environment through the intake and exhaust galleries shall be
considered:

frozen portion c-1: gas intake in the

of gas IVpe2
intake
cylinder:
pe1=p1 p = ct = pe,1 = pe,2
1: the inlet valve is closed
1-2: the release of the gas
pe2=p2
exit from p1 to p2
EV 2-d: opening of the exit
valve: discharge of gas to
P p = ct = pe,2 = p2
dm>0 1
pe,1=p1 c I
Mechanical work performed in
sa
dm=0 this sequence of processes =
technical or total work or
pe,2=p2 d mechanical work collected on the
dm<0 2
machine shaft.
a b V
Prof. Monica Costea - Lecture 4_First Law (1) 29

• For an infinitely small process:

δWsh,e = δWe – d(peV) = pedV- pedV - Vdpe => δWsh,e = – Vdpe
• For a reversible process, the p inside differs only by a small
infinity from the external pressure pe:
pe,1 = p1 + dp
It results: δWsh = – Vdp , p = gas pressure in the system
Reversible processes can be represented in the p-V diagram, the
corresponding area Wsh being:
Wsh,1-2 = Wc-2 + W1-2 + W2- d = area (0c1a0) + area (a12ba) –
area (0d2b0) = area (c12dc)
=> in the p-V diagram, Wsh is represented by the area between the
process curve and the ordinate axes.
Sign: δWsh = – Vdp => dp > 0 Wsh → < 0 (compression: Wsh-)
dp < 0 Wsh → > 0 (expansion: Wsh+)

3.2. Heat. Specific heats

Heat = the macroscopic form of energy transfer between bodies

due to the finite temperature difference between them.
- It is not a state property, but a process one (path function);
- There is no notion of " infinitely small variation of heat", but
only of "infinitely small quatity of heat" - δQ
For a finite heat exchange process we have:
2
Q1− 2 =  Q
1

The heat is proportional to the mass of the body and T (from

experiences, in heating/cooling processes), the proportionality
factor being the specific heat.
Prof. Monica Costea - Lecture 4_First Law (1) 30

Small inf. amount of heat taken over/ceded by a body:

δQ = m c dT, with c-true specific heat
Q1-2=m c (T2-T1) [J]

Sign: dT>0 →δQ>0 Q → received

dT<0 →δQ<0 Q → rejected
dT=0 →δQ=0 → isothermal process

Specific heat = energy required torise the temperature of a unit

mass of a substance by one degree.
It is a property of the substance that depends on:
a) quantity;
b) process;
c) temperature, that influences the specific heat of all substances;
d) pressure, which has a lower influence, except for vapour;
e) nature of the substance.
a) Dependence on quantity unit
To express the amount of gas are used as units: kg, kmol, m3N.
Correspondingly, one has:
δQ = m c dT with c [J/(kgK)], mass-specific heat
δQ = m CM dT with CM [J/(kmolK)], molar-specific heat
δQ = m CN dT with CN [J/(m3NK)], specific heat relative to m3N
Relations:
C C
c= M = N M – molar mass [kg/kmol]
M N
CM = cM = CNVM,N N – density in the normal state
C cM
CN = M = = c N VM,N = 22,414 m3N/kmol
VM , N VM , N
VM,N – molar volume in the normal state
Prof. Monica Costea - Lecture 4_First Law (1) 31

b) Dependence on the process

- V = ct → cV: specific heat at constant volume, cV > 0
- p = ct → cp: specific heat at constant pressure, cp > 0
- T = ct → cT: isothermal-specific heat, cT → ± 
- Q = 0 → cad: adiabatic specific heat, cad = 0;
- polytropic → cn: polytropic specific heat, cn >< 0, as n(-,+)
c
OBS: k = p = adiabatic exponent, with cp > cV
cV
 k is always > 1