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First Law of Thermodynamics for a Closed System

This is a topic from Thermodynamics:
Contents
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1 Statement
1.1 Stationary Systems
2 Internal Energy
3 Specific Heat Capacity CV
4 Enthalpy
5 Specific Heat Capacity CP
6 Relating CV and CP
6.1 Relation with the Gas Constant
6.2 The Isentropic Index
6.3 Combining Relations
7 Common Application of Enthalpy in Problem Solving

Statement
The 1st Law of Thermodynamics for a closed system states that:
Ein - Eout = ESystem
It is a basic implication of the law of conservation of energy, and as such requires no derivation.
The right hand side:
ESystem = EInternal + EKinetic + EPotential
=m(u2 - u1) + m((v2)2 - (v1)2)/2 + mg(z2 - z1)
where z represents height (we
u represents specific internal energy.

don't

use

The left hand side:

Taking into account heat transfer only:
Ein - Eout = Q12
Taking into account work transfer only:
Ein - Eout = -W12
Thus taking both heat and work into account:
Ein - Eout = Q12 - W12
Therefore the law can be rewritten in full as:
Q12 - W12 = m(u2 - u1) + m((v2)2 - (v1)2)/2 + mg(z2 - z1)

'h'

here,

because

'h'

represents

enthalpy)

Stationary Systems
It is very common for a problem to involve a system which is stationary. For a stationary system the change
in the kinetic energy and potential energy are zero, and so:
Q12 - W12 = m(u2 - u1) and
dQ - dW = dU
This
is
the
most
common
form
of
the
first
law
in
this
course.
In order to apply the first law of thermodynamics to problems we must first explore the concept of internal
energy, as well as the related concept, enthalpy.

Internal Energy
Internal energy is a property, the unit of which is the joule.
It is a measure of the energy associated with the random, molecular motion of a substance due to its
temperature. Therefore the internal energy is the sum of the microscopic internal kinetic and potential
energy of the molecules which make up a system, as opposed to the macroscopic kinetic and potential
energy of the system itself.
It follows that the internal energy of a system is linearly proportional to the amount of matter in the system its mass- as well as the temperature of the system:
U mT
U/m T
uT
The symbol is the Greek letter alpha and means 'directly proportional to'
This constant of proportionality is known as the specific heat capacity

Specific Heat Capacity CV

Specific heat capacity is the energy required to increase the temperature of one kilogram of some
substance by one degree.
The magnitude of the specific heat capacity is always based on one kilogram, not the extent of the system,
and so specific heat capacity is an intensive property (as are all 'specific' properties).
Specific heat capacity for a heat transfer which occurs at constant volume is represented by C V
If heat is transferred to or from a substance at a constant volume, then:
CV = du/dT
du = CV dT
Integrating both sides:

Multiplying both sides by mass changes specific internal energy to internal energy:

This change in internal energy is irrespective of the type of process which caused the temperature change.

Enthalpy
Enthalpy is a property, defined in relation to other existing properties, including internal energy:
Enthalpy = Internal Energy + Pressure x Volume
H = U + PV
The unit of enthalpy is the joule, because:

and decomposing with S.I units:

and so enthalpy is the sum of two energy properties.

Thus, even though enthalpy's definition is based on other properties, it can be defined in its own right as a
measure of the total energy of a stationary thermodynamic system, including the internal energy of a
substance and the amount of energy required to make room for it by displacing its environment and
establishing its volume and pressure.

Specific Heat Capacity CP

The definition of specific heat capacity for a constant pressure process arises from an examination of the
definition of enthalpy.
Dividing both sides of the definition for enthalpy by mass gives:
H/m = U/m + PV/m
h = u + Pv
where h, u and v are specific heat, specific internal energy and specific volume respectively.
By the ideal gas law, Pv = RT, and so:
h = u + RT
Since internal energy is a function of temperature, enthalpy is the sum of two functions of temperature, and
so:
hT
Having established this proportionality the same method can be applied to derive C P as with CV.
Thus if heat is transferred to or from a substance at constant pressure:
CP = dh/dT
dh = CPdT
Integrating both sides:

Multiplying both sides by mass changes specific internal energy to internal energy:

Relating CV and CP
Relation with the Gas Constant
The two constants can be related using the definitions of specific enthalpy and the ideal gas law:
(1) h = u + Pv
(2) Pv = RT
Writing these definitions in differential form:
(1) dh =du + Pdv
(2) Pdv = RdT
Substituting (1) into (2):
dh = du + RdT
Dividing both sides by dT:
dh/dT = du/dT + R
Recalling the respective definitions of CP and CV:
CP = CV + R

The Isentropic Index

The isentropic index or ratio of specific heat capacities is represented by k or :
k = = CP/CV

Combining Relations
Combining these two relations leads to some useful expressions.
Rearranging the isentropic index:
CVk = CP
CV = CP/k
Substituting into the gas constant relation:
CP = CP/k + R
CP(1 - 1/k) = R
CP(k-1)/k = R
Therefore:

CP = kR/(k-1)
And since CV = CP/k:
CV = R/(k-1)

Common Application of Enthalpy in Problem Solving

Considering an isobaric process (constant pressure) for a stationary system, find the heat transfer, Q.
The first law states that Q12 - W12 = U12
Substituting the formula for work for an isobaric process (W12 = P(V2 - V1)):
Q12 - P(V2 - V1) = (U2 - U1)
Rearranging gives:
Q12 = (U2 + PV2) - (U1 + PV1)
Recalling the definition of enthalpy:
Q12 = H2 - H1
= H
From our analysis of specific heat for constant pressure, H = mCP(T2 - T1), and so:
Q12 = mCP(T2 - T1)