Energy Balance

Energy Balance
BT2061: Biochemical Thermodynamics
M. Hamsa Priya
M. Hamsa Priya BT2061:EB 1 / 18

Energy Balance
First Law of Thermodynamics
Energy is a conserved quantity – It can neither be created nor

destroyed, only gets transformed from one form to another.

Energy Balance

Total energy of a system

Energy Balance

Total energy of a system is the sum of internal energy, kinetic energy
and potential energy of the system
1
E = U + Mv 2 + Mψ ,
2
where, 21 v 2 is the kinetic energy per unit mass and ψ is the potential
energy per unit mass. If gravity is the only force field, ψ = gh

Energy Balance
Energy Balance Equation – Mathematical Form of First

Law
Recollect General Balance Equation

   
Rate of change Rate at which θ
 of θ in the system  =  flows in/out of 
i.e., Accumulation the system
 
Rate at which θ
+  is generated/consumed 
within the system
dθ X
= θ̇k + rθ
dt
k

Energy Balance

Law
Accumulation:
dE d 1
= U + Mv2 + Mψ
dt dt 2
Energy flow accompanying mass flows:

X 1
Ṁk Û + v2 + ψ ,
2 k
k
where, Ûk – specific internal energy i.e., internal energy per unit mass
of kth stream

Energy Balance

Law
Other energy transfer modes:

Energy Balance

Law
Heat Transfer: Rate of flow of heat into the system = Q̇
Sign Convention: Heat into the system – Positive; Heat liberated by
the system – Negative

Energy Balance

Law
Heat Transfer: Rate of flow of heat into the system = Q̇
Sign Convention: Heat into the system – Positive; Heat liberated by
Work: There are two forms of work
Shaft work, Ẇs – No deformation of system boundary
Pressure volume work – Due to movement of system boundary
dV
Ẇ ≡ −P
dt
Sign Convention: Work done onto the system – positive; work done by
Work of a flowing fluid against pressure
X
Ṁk (PV̂k )
k

Energy Balance

Law
Workdone by the surrounding fluid in pushing fluid element of mass

∆M1 into the system = P1 V̂1 ∆M1
Workdone on the surrounding fluid by the movement of fluid element
of mass ∆M2 out of the system = - P2 V̂2 ∆M2
Net work done on the system = P1 V̂1 ∆M1 − P2 V̂2 ∆M2
Net rate at which work is done on the system due
Xto pressure forces
acting on fluids moving in/out of the system = Ṁk (PV̂)k
k

Energy Balance

Law
Energy Balance Equation:
X
d 1 2 1 2
U + Mv + Mψ = Ṁk Û + v + ψ +
dt 2 2 k
k
dV X
Q̇ + Ẇs − P + Ṁk (PV̂)k
dt
k
Usually kinetic and potential energy terms are small compared to the
internal energy, unless the fluid velocity is near the velocity of sound,
the change in height is very large
Let’s introduce the term Enthalpy (H):
H ≡ U + PV
Ĥ ≡ U + PV̂
Energy Balance

Law
Energy Balance Equation:

dU X dV
= Ṁk Ĥk + Q̇ + Ẇs − P
dt dt
k
Energy Balance Equation (Molar basis):
dU d X dV
= (NU) = Ṅk Hk + Q̇ + Ẇs − P
dt dt dt
k

Energy Balance
Exercise
Write the Energy Balance Equation for the following cases

Closed system
Closed system with rigid system wall
Adiabatic system
Open system under steady state condition

Energy Balance
Exercise
A mass M of gas is to be compressed from a temperature T1 and a

pressure P1 to T2 and P2 .
In one step process in a frictionless piston and cylinder assembly
In a continuous steady state process in which the mass M of gas is a
part of the feed stream to the compressor
Compute Q + W for each process

Energy Balance
A Brief Introduction to Thermodynamics Properties of

Matter
To solve thermodynamic problems, one needs to know

Relationship between T, P and V or V

Energy Balance

Matter

Relationship between T, P and V or V – Volumetric Equation of State

Energy Balance

Matter

Relationship between {T, P, V} and {U, H}

Energy Balance

Matter

Relationship between {T, P, V} and {U, H} – Thermal Equation of
State

Energy Balance
Volumetric Equation of State
Simplest volumetric equation of state

Energy Balance

Ideal gas Equation of State:
PV = RT
or
PV = NRT

Energy Balance

PV = RT
or
PV = NRT
What is an ideal gas?

Energy Balance

PV = RT
or
PV = NRT

Each gaseous molecule is only a point mass
No interaction among molecules
Does any gas, you know, obeys these two condition of ideal gas?

Energy Balance

PV = RT
or
PV = NRT

Why to study about ideal gas?

Energy Balance

PV = RT
or
PV = NRT

Why to study about ideal gas?
All gas at very low pressure is believed to act like an ideal gas

Energy Balance
Thermal Equation of State
For an ideal gas

U = U(T)
H = H(T)
For real gases
U = U(T, V)
H = H(T, P)

Energy Balance
Constant Volume Heat Capacity Cv
Definition:

Energy Balance
Constant Volume Heat Capacity Cv
Definition: Amount of heat required to raise the temperature of a

substance by 1◦ C at constant volume.

∂U
CV (T, V) =
∂T V
Change in internal energy:

For real gases:
Z T2
∆U = U(T2 , V) − U(T1 , V) = CV (T, V)dT
T1
For an ideal gas:

Z T2
∆U = U(T2 ) − U(T1 ) = C∗V (T)dT
T1

Energy Balance
Constant Pressure Heat Capacity CP
Definition:

Energy Balance
Constant Pressure Heat Capacity CP
Definition: Amount of heat required to raise the temperature of a

substance by 1◦ C at constant pressure.

∂H
CP (T, P) =
∂T P
Change in enthalpy:
For real gases:
Z T2
∆H = H(T2 , P) − H(T1 , P) = CP (T, P)dT
T1
For an ideal gas:

Z T2
∆H = H(T2 ) − H(T1 ) = C∗P (T)dT
T1

Energy Balance
C∗P as the function of temperature
C∗P may be constant or a function of temperature
C∗P (T) = a + bT + cT2 + dT3 + . . .

Energy Balance
C∗V as the function of temperature
C∗P (T) is obtained from Appendix II

How to obtain C∗V (T)?

Energy Balance

dH dU + PV
C∗P = = = C∗V + R
dT dT

Energy Balance

dH dU + PV
C∗P = = = C∗V + R
dT dT
Thus,
C∗V (T) = C∗P (T) − R = (a − R) + bT + cT2 + dT3 + . . .

Energy Balance
Latent Heat Associated with Phase Change

What is latent heat?

Energy Balance

Latent heat of vaporization
∆vap Ĥ = ĤV − ĤL
∆vap H = HV − HL

Energy Balance

Latent heat of fusion:

∆fus H = HL − HS

Energy Balance

Latent heat of fusion:

∆fus H = HL − HS
Latent heat of sublimation:

∆sub H = HV − HS
For solids and liquids at low pressure, as molar volumes of the
condensed phase is small

∂V
H = U; =0
∂P T

Energy Balance

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Energy Balance

BT2061: Biochemical Thermodynamics

M. Hamsa Priya BT2061:EB 1 / 18

First Law of Thermodynamics

Energy is a conserved quantity – It can neither be created nor

M. Hamsa Priya BT2061:EB 2 / 18

First Law of Thermodynamics

Energy is a conserved quantity – It can neither be created nor

M. Hamsa Priya BT2061:EB 2 / 18

First Law of Thermodynamics

Energy is a conserved quantity – It can neither be created nor

M. Hamsa Priya BT2061:EB 2 / 18

Energy Balance Equation – Mathematical Form of First

Recollect General Balance Equation

M. Hamsa Priya BT2061:EB 3 / 18

Energy Balance Equation – Mathematical Form of First

M. Hamsa Priya BT2061:EB 4 / 18

Energy Balance Equation – Mathematical Form of First

M. Hamsa Priya BT2061:EB 5 / 18

Energy Balance Equation – Mathematical Form of First

M. Hamsa Priya BT2061:EB 5 / 18

Energy Balance Equation – Mathematical Form of First

M. Hamsa Priya BT2061:EB 5 / 18

Energy Balance Equation – Mathematical Form of First

Workdone by the surrounding fluid in pushing fluid element of mass

M. Hamsa Priya BT2061:EB 6 / 18

Energy Balance Equation – Mathematical Form of First

Energy Balance Equation – Mathematical Form of First

Energy Balance Equation:

Energy Balance Equation (Molar basis):

M. Hamsa Priya BT2061:EB 8 / 18

Write the Energy Balance Equation for the following cases

M. Hamsa Priya BT2061:EB 9 / 18

A mass M of gas is to be compressed from a temperature T1 and a

M. Hamsa Priya BT2061:EB 10 / 18

A Brief Introduction to Thermodynamics Properties of

To solve thermodynamic problems, one needs to know

M. Hamsa Priya BT2061:EB 11 / 18

A Brief Introduction to Thermodynamics Properties of

To solve thermodynamic problems, one needs to know

M. Hamsa Priya BT2061:EB 11 / 18

A Brief Introduction to Thermodynamics Properties of

To solve thermodynamic problems, one needs to know

M. Hamsa Priya BT2061:EB 11 / 18

A Brief Introduction to Thermodynamics Properties of

To solve thermodynamic problems, one needs to know

M. Hamsa Priya BT2061:EB 11 / 18

Volumetric Equation of State

Simplest volumetric equation of state

M. Hamsa Priya BT2061:EB 12 / 18

Volumetric Equation of State

Simplest volumetric equation of state

M. Hamsa Priya BT2061:EB 12 / 18

Volumetric Equation of State

Simplest volumetric equation of state

What is an ideal gas?

M. Hamsa Priya BT2061:EB 12 / 18

Volumetric Equation of State