Thermodynamics

Ashok Kumar Dasmahapatra

Department of Chemical Engineering, Indian Institute of Technology Guwahati

First Law of Thermodynamics
First Law of Thermodynamics

 Background: Joule’s experiment

 Internal Energy
 First Law of Thermodynamics – Conservation of Energy
 Closed system – Energy balance
 Thermodynamic Sate and State Functions
 Equilibrium – Phase Rule
 Reversible Process – chemical reaction
 Constant Volume and Constant Pressure Processes
 Enthalpy
 Heat Capacity – Constant Volume and Constant Pressure
 Open system – Mass and Energy Balance
 Energy Balance for Steady State Flow Processes, Flow
calorimeter
First Law of Thermodynamics
Background: Joule’s experiment

Known amount of water, oil and mercury in an insulated container

Agitated the container with a stirrer
Work done on the fluid by the stirrer
Change in temperature recorded
A certain amount of work is required per unit mass of fluid to
increase one degree temperature
 Quantitative relationship between work and heat
 Heat is one form of ENERGY
First Law of Thermodynamics
Internal Energy
Joule’s experiment – energy (work) added to the fluid  transferred as
heat.
Internal energy: Energy possessed internally by a molecules,
independent of externally added energy (heat).
Random motion, rotation, vibration  kinetic energy
Externally added heat increases these motions  causes in increase in
internal energy

Potential energy: it is also a form of internal energy, arises due to

intermolecular interactions

It cannot be measured directly, no such internal energy meters!

There is not absolute value of this, only difference is more important for
all practical purposes.
First Law of Thermodynamics
First Law of Thermodynamics – Conservation of Energy
A formal statement:

System and Surroundings:

Control
volume
System: the region in which the process occurs
Surroundings: Everything else except the system,  System
the system interacts with the surroundings

First law takes into account both the system Surroundings

and surroundings:

∆ 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒚𝒔𝒕𝒆𝒎 + ∆ 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 = 𝟎 −− −(𝟏)

D refers to a finite change

First Law of Thermodynamics
Closed system – Energy balance 𝑸
Control
Closed system: volume

System 𝑾

Surroundings

 Mass of the system remains constant throughout the process

 No mass entering/leaving  no energy associated with the ‘mass’ is involved
 All energy change between a system and its surroundings  heat and work
 The second term of Equation (1) can be written as:
∆ 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 = ±𝑸 ± 𝑾 −− −(𝟐)

 Change in energy of the surroundings  net change in the energy

transferred to and from it in the form of heat and work of the system
 Sign convention:
 Positive: if the transfer happens into the system from the surroundings
 Negative: from system into surroundings
First Law of Thermodynamics
Closed system – Energy balance
∆ 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 = ±𝑸 ± 𝑾 −− −(𝟐)

Positive: if the transfer happens into the system from the surroundings
Negative: from system to surroundings

Here, Qsurr = -Q and Wsurr = -W

∆ 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 = −𝑸 − 𝑾 −− −(𝟑)

For the system: 𝑸

Control
∆ 𝑬𝒏𝒆𝒓𝒈𝒚 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒚𝒔𝒕𝒆𝒎 = 𝑸 + 𝑾 − −(𝟒)
volume

System 𝑾
Combination of eq. (3) and (4)
 total energy change of a closed system equals Surroundings
the net energy transferred into it as heat and work
First Law of Thermodynamics
Closed system – Energy balance
The process, where only internal energy changes:
The change in total internal energy of the system:

∆ 𝑼𝒕 = 𝑸 + 𝑾 −− −(𝟓)

For differential changes, we can write: U  internal energy per

mole of a substance
𝒅𝑼𝒕 = 𝒅𝑸 + 𝒅𝑾 −− −(𝟔)

For a closed system with n moles:

∆ 𝒏𝑼 = 𝒏∆𝑼 = 𝑸 + 𝑾 −− −(𝟕) From equation (5)

𝒅 𝒏𝑼 = 𝒏𝒅𝑼 = 𝒅𝑸 + 𝒅𝑾 −− −(𝟖) From equation (6)

 Connects the internal energy to measurable quantities, and relates all other properties
 Internal energy is an intrinsic property of a system
First Law of Thermodynamics
Thermodynamic State and State Functions
∆ 𝒏𝑼 = 𝒏∆𝑼 = 𝑸 + 𝑾 −− −(𝟕) 𝒅 𝒏𝑼 = 𝒏𝒅𝑼 = 𝒅𝑸 + 𝒅𝑾 −− −(𝟖)

In the above equations, quantities on the left represents the changes in the
thermodynamic state of a system
Governed by the thermodynamic properties, such as T, P, Density.

State functions: Quantities, whose change depends on the present conditions only, not
depend on the past history.

In the above equations, quantities on the right depend on the nature of the process
The differential of a state function represents an infinitesimal change in its value.
Integration of such differential would give a finite difference between two of its value:
𝑃2 𝑉2
𝑑𝑃 = 𝑃2 − 𝑃1 = ∆𝑃 𝑉1
𝑑𝑉 = 𝑉2 − 𝑉1 = ∆𝑉
𝑃1

The differential of heat and work represents a finite change in its value.
Integration of such differential would give a finite amount:

𝑑𝑄 = 𝑄 𝑑𝑊 = 𝑊
First Law of Thermodynamics
Equilibrium – Phase Rule

Equilibrium – no change in macroscopic scale with time

 Absence of driving force to cause the change

 Different driving forces for different transfer processes:

 Examples: temperature difference in heat transfer;
difference in chemical potential in mass transfer;
difference in pressure in fluid flow, etc.

Difference between STEADY STATE and EQUILIBRIUM

STEADY STATE – driving force exists, EQUILIBRIUM – no net driving force

F: degrees of freedom
Gibbs Phase Rule: 𝐹 =𝑁−𝜋+2 N: numbers of components
p: numbers of phases
2: T and P

Number of independent variables for a given system in relation with its intensive state
First Law of Thermodynamics
Equilibrium – Phase Rule
Phase rule variables: T, P, compositions.
They are not all independent
Phase rule variables are intensive properties

Phase: a homogeneous region of a matter (gas, liquid, etc.)

The minimum number of degrees of freedom of any system = 0

 There is NO independent variables exists in the system

𝐹 =0=𝑁−𝜋+2→𝜋 =𝑁+2 Maximum number of phases

which can coexist at equilibrium,
with N chemical species

For N = 1, 𝜋 = 3  triple point (𝐹 = 0)

First Law of Thermodynamics
 Reversible Process – chemical reaction
A process is reversible when its direction can be reversed at
any point by an infinitesimal change in external conditions.

Reversible Expansion of a Gas

A gas cylinder with a piston, gas inside the cylinder is the system

m = a mass that keeps the system in equilibrium

Addition/removal of mass (m) will make the piston move

downward/upward, attain a new equilibrium state.

The piston is assumed to be friction less

For mechanically reversible process, work done can be given by:

𝑉2
𝑊=− 𝑉1
𝑃·dV
First Law of Thermodynamics
 Reversible Process – chemical reaction
A process is reversible when its direction can be reversed at
any point by an infinitesimal change in external conditions.

Reversible Chemical Reaction

Decomposition of CaCO3: 𝑪𝒂𝑪𝑶𝟑 ⇌ 𝑪𝒂𝑶 + 𝑪𝑶𝟐

Decomposition equilibrium depends on the applied pressure, assuming a closed system

at a constant temperature
Balance between pressure of CO2 and applied external pressure

Reversible process:
Frictionless, never more than differentially removed from equilibrium
Traverses a succession of equilibrium states
Driven by forces whose imbalance is differential in magnitude
Can be reversed at any point by a differential change in external conditions
When reversed, retraces its forward path, and restores the initial state of system and
surroundings.
First Law of Thermodynamics
 Reversible Process – chemical reaction
A process is reversible when its direction can be reversed at
any point by an infinitesimal change in external conditions.

Microscopic and Macroscopic Reversibility

Hysteresis loop

Macroscopic reversible Irreversible Microscopic reversible

Which process is reversible and which is irreversible?

First Law of Thermodynamics
 Constant Volume and Constant Pressure Processes
For n moles of a homogeneous fluid in a closed system, the energy balance is:

𝑑 𝑛𝑈 = 𝑑𝑄 + 𝑑𝑊 ………………. (9) Q: Total heat

W: Total work

For a mechanically reversible, closed system process, the work W is given by:

𝑑𝑊 = −𝑃𝑑(𝑛𝑉) ………………. (10)

Combining eq. (9) and eq. (10): 𝑑 𝑛𝑈 = 𝑑𝑄 − 𝑃𝑑(𝑛𝑉) ………………. (11)

 Equation (11) is a general energy balance equation

for n moles of a homogeneous fluid in closed system
First Law of Thermodynamics
 Constant Volume Processes
𝑑 𝑛𝑈 = 𝑑𝑄 − 𝑃𝑑(𝑛𝑉) ………………. (11)
For a constant volume process, dV = 0

𝑑 𝑛𝑈 = 𝑑𝑄 ………………. (12)
 𝑸 = 𝒏∆𝑼 … … … … … 13

Heat transferred in a mechanically reversible system, at constant volume,

closed system process = change in internal energy of the system.

 Constant Pressure Processes

𝑑 𝑛𝑈 = 𝑑𝑄 − 𝑃𝑑(𝑛𝑉) ………………. (11)

Rearranging:
𝑑𝑄 = 𝑑 𝑛𝑈 + 𝑃𝑑(𝑛𝑉)

For a constant pressure system (volume is variable): 𝑼 + 𝑷𝑽 = 𝑯 (Enthalpy)

𝑑𝑄 = 𝑑 𝑛𝑈 + 𝑑 𝑛𝑃𝑉 = 𝑑 𝑛 𝑼 + 𝑷𝑽 … … . . (14)

 𝒅𝑸 = 𝒅 𝒏𝑯  𝑸 = 𝒏∆𝑯 … … (15)
First Law of Thermodynamics
 Enthalpy (H)
𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉) …………. (16) U, P, V  all are state functions
 H is also a state function

Units: U – energy per mole; (PV) – energy per mole; H – energy per mole

PV: (N m-2)(m3 mol-1) = (N m) mol-1 = Joule mol-1

Integrating eq. (16), gives finite change into the system:

∆𝐻 = ∆𝑈 + ∆(𝑃𝑉) …………. (17)
First Law of Thermodynamics
 Heat Capacity – Constant Volume and Constant Pressure
𝑑𝑄
𝐶=  Change in heat by change in temperature ……………….. (18)
𝑑𝑇

 Heat Capacity – Constant Volume Pressure

Closed system 𝑑 𝑛𝑈 = 𝑑𝑄 ………………. (12)
𝑑𝑈
𝐶𝑣 = ………………(19)  𝑸 = 𝒏∆𝑼 … … … … … 13
𝑑𝑇 𝑣

𝑑𝑈 = 𝐶𝑣𝑑𝑇

𝑇2
 ∆𝑈 = 𝐶 𝑑𝑇
𝑇1 𝑣
… … … . (20)

For a mechanically reversible process at constant volume:

𝑇2
𝑄 = 𝑛∆𝑈 = 𝑛 𝐶 𝑑𝑇
𝑇1 𝑣
… … … . (21)
First Law of Thermodynamics
 Heat Capacity – Constant Pressure Pressure
𝑑𝐻 Closed system
𝐶𝑝 = ………………(22)
𝑑𝑇 𝑝
𝒅𝑸 = 𝒅 𝒏𝑯  𝑸 = 𝒏∆𝑯 … … (15)
𝑑𝐻 = 𝐶𝑝𝑑𝑇

𝑇2
 ∆𝐻 = 𝐶 𝑑𝑇
𝑇1 𝑝
… … … . (23)

For a mechanically reversible process at constant volume:

𝑇2
𝑄 = 𝑛∆𝐻 = 𝑛 𝐶 𝑑𝑇
𝑇1 𝑝
… … … . (24)

Remarks on constant V and P:

 For a multiple steps process, V varies form one step to the other
 The system returns to the initial state, net DV = 0
 Changes in the state functions are path-independent, and can be calculated by taking
volume constant (Vi = Vf); one can use: ∆𝑈 = 𝑛 𝐶𝑣 𝑑𝑇, since U, Cv and T are all state
functions.
 For the calculation of property changes, an actual process may be replaced by any other
process, which accomplishes the same change in state.
 A similar argument is equally hold good for P.
First Law of Thermodynamics
 Open system – Mass and Energy Balance
Measures of flow: 𝑀 = Molar mass
𝑚 = mass flow rate (mass/unit time) 𝑚 = 𝑀𝑛
𝑛 = molar flow rate (mol/unit time) 𝑞 = uA
𝑚 = uAρ Specific density
𝑞 = volumetric flow rate (vol/unit time)
𝑣 = velocity (distance/unit time) 𝑛 = uAρ
Molar density

𝒎1
Mass Balance for Open System: 𝒎3
Control volume  system Control
𝒎1 and 𝒎2  inward flow volume
𝒎3  outward flow
Since, total mass is conserved, there will be
change in mass in the control volume, dmcv/dt
𝒎2 Control
Convention: (+ve), if mass flows into the system, surface
and (-ve) if mass flows out of the system
Mass balance:
Net change in the mass flow rate:
𝒅𝒎𝒄𝒗
∆ 𝑚 𝑓𝑠 = 𝑚3 − 𝑚1−𝑚2 ---- (25) +∆ 𝒎 𝒇𝒔 = 𝟎 … . (𝟐𝟔)
𝒅𝒕
First Law of Thermodynamics
 Open system – Mass and Energy Balance
Mass balance: 𝒎1 𝒎3
𝒅𝒎𝒄𝒗 Control
+ ∆ 𝒎 𝒇𝒔 = 𝟎 …….(26) volume
𝒅𝒕

𝒅𝒎𝒄𝒗
+ (𝑚3 − 𝑚1−𝑚2) = 𝟎 … … (𝟐𝟕)
𝒅𝒕

𝒅𝒎𝒄𝒗 Continuity equation 𝒎2 Control

+ ∆ 𝐮𝐀𝝆 𝒇𝒔 = 𝟎 … . . (𝟐𝟖) surface
𝒅𝒕

Steady state: no accumulation in the control volume

∆ uAρ 𝒇𝒔 = 𝟎 … . . (𝟐𝟗)

For ONE entry and ONE exit stream, equation (29) gives:
𝒖𝟏 𝑨𝟏 𝒖𝟐𝑨𝟐 𝒖𝑨
𝐮𝟐𝐀𝟐𝝆𝟐 = 𝐮𝟏𝐀𝟏𝝆𝟏 = 𝒎 = 𝐜𝐨𝐧𝐬𝐭 … . (𝟐𝟗) 𝒎= 𝑽𝟏
= 𝑽𝟐
= 𝑽
….. (30)
First Law of Thermodynamics
 Open system – Mass and Energy Balance
Energy balance: 𝒎2
Potential 𝑸 u2
Mass flow rate: 𝑚 Control
energy volume
Total energy associated:
𝟏 𝟐 𝑾
𝑼 + 𝒖 + 𝒛𝒈 𝒎 … … (𝟑𝟏)
𝟐
𝒎1 Control
Internal Kinetic
energy u1 surface
energy

The net energy transported into the system (in – out)

𝟏
−∆ 𝑼 + 𝒖𝟐 + 𝒛𝒈 𝒎 𝒇𝒔 … … (𝟑𝟐)
𝟐

Energy Accumulation:
Heat transfer rate: 𝑸
𝒅(𝒎𝑼)𝒄𝒗 𝟏
Work rate: 𝑾 = −∆ 𝑼 + 𝟐 𝒖𝟐 + 𝒛𝒈 𝒎 𝒇𝒔 + 𝑸 + 𝑾 ….. (33)
𝒅𝒕
First Law of Thermodynamics
 Open system – Mass and Energy Balance
Energy balance: 𝒎2
𝑸 u2
Work rate: 𝑾 Control
volume

Work done: PV, for a mechanical system, 𝑾

at a pressure P and volume V
Change in work: −∆ 𝑷𝑽 𝒎 𝒇𝒔
𝒎1 Control
Other form of work: shaft work, 𝑾𝒔 ≈ 𝑾
u1 surface

Energy Accumulation incorporating above work rates:

𝒅(𝒎𝑼)𝒄𝒗 𝟏
= −∆ 𝑼 + 𝟐 𝒖𝟐 + 𝒛𝒈 𝒎 𝒇𝒔 + 𝑸 − ∆ 𝑷𝑽 𝒎 𝒇𝒔 + 𝑾 ….. (34)
𝒅𝒕

𝑬𝒏𝒕𝒉𝒂𝒍𝒑𝒚, 𝑯 = 𝑼 + 𝑷𝑽
𝒅(𝒎𝑼)𝒄𝒗 𝟏
= −∆ 𝑯 + 𝟐 𝒖𝟐 + 𝒛𝒈 𝒎 𝒇𝒔 + 𝑸 + 𝑾 ….. (35)
𝒅𝒕

𝒅(𝒎𝑼)𝒄𝒗 𝟏
+ ∆ 𝑯 + 𝟐 𝒖𝟐 + 𝒛𝒈 𝒎 𝒇𝒔 = 𝑸 + 𝑾 ….. (36)
𝒅𝒕
First Law of Thermodynamics
 Open system – Mass and Energy Balance
𝒎2
Energy balance: 𝑸 u2
Control
volume
𝒅(𝒎𝑼)𝒄𝒗 𝟏
+ ∆ 𝑯 + 𝟐 𝒖𝟐 + 𝒛𝒈 𝒎 𝒇𝒔 = 𝑸 + 𝑾 ….. (36)
𝒅𝒕
𝑾

𝒖: bulk mean velocity, 𝒖 = 𝒎 𝑨𝝆

𝒎1 Control
u1 surface

Special Case: change in kinetic and potential energy negligible:

𝒅(𝒎𝑼)𝒄𝒗
+ ∆ 𝑯𝒎 𝒇𝒔 = 𝑸 + 𝑾 ….. (37)
𝒅𝒕
First Law of Thermodynamics
 Energy Balance for Steady State Flow Processes
Energy balance:
𝒅(𝒎𝑼)𝒄𝒗 𝟏
+ ∆ 𝑯 + 𝟐 𝒖𝟐 + 𝒛𝒈 𝒎 𝒇𝒔 = 𝑸 + 𝑾 ….. (36)
𝒅𝒕

For a steady-state process, the accumulation term = 0

𝒅(𝒎𝑼)𝒄𝒗
 =𝟎
𝒅𝒕
𝟏
∆ 𝑯 + 𝟐 𝒖𝟐 + 𝒛𝒈 𝒎 𝒇𝒔 = 𝑸 + 𝑾 ….. (38)

𝟏 𝑸 𝑾
Dividing by 𝒎: ∆ 𝑯 + 𝟐 𝒖𝟐 + 𝒛𝒈 𝒇𝒔 = 𝒎 + = 𝑸 + 𝑾 ….. (39) (Energy/unit mass)
𝒎

Mathematical statement of the First law for

∆𝒖𝟐
∆𝑯 + + 𝒈∆𝒛 = 𝑸 + 𝑾 ….. (40) a steady state, steady flow process with
𝟐
one entry and one exit

In many processes, kinetic and potential energies are negligible compared to the rest:

∆𝑯 = 𝑸 + 𝑾 ….. (41) Similar to eq. (40) without flow

First Law of Thermodynamics
 Summary

 The first law of thermodynamics, appropriate sign conventions

 The concepts of internal energy, enthalpy, state function, equilibrium, and
reversible process
 Differences between state functions and path-dependent quantities such as
heat and work
 Changes in state variables for a real process by substituting a hypothetical
reversible process connecting the same states
 Changes in the internal energy and enthalpy of a substance with change in
temperature
 Heat capacity
 Mass and energy balances for open systems
First Law of Thermodynamics
 Flow Calorimeter

Self-Study Assignment

Go through the Solved problems

First Law of Thermodynamics

Tutorial Problems

Smith, Van Ness, 8th Edition

2.6, 2.8, 2.9, 2.10, 2.19, 2.24, 2.25, 2.26, 2.30, 2.34