LG 5.

First
First Law
Law of
of Thermodynamics
Thermodynamics
I n t e r Internal
n a l E n e r g
y
Internal Energy Energy
- The sum of the kinetic and potential energies of its constituent particles.

Key points:
• Heat transferred to an object increases the kinetic and/or potential energy of its constituent
particles.
• Heat transferred To an object increases its internal energy.
• Heat extracted to an object decreases its internal energy.
• Internal energy is an increasing function of temperature.

Formulas:

Kinetic Energy (J):

m – mass (kg)
1  K = mv2
v – speed (m/s)

2  K = NkT N – no. of particles in the gas

T – temperature (K)
k = 1.38 x 10-23 J/K (Boltzmann
constant)

Potential Energy (J):

3 U = mgh m = mass (kg)

g = 9.8 m/s (gravity)
h = height (m)
LG 5.2

First Law
First Law of
of Thermodynamics
Thermodynamics
Work
Thermodynamic Work
- The average work done by a system composed of many particles to its surroundings.
- It is path-dependent (nonconservative)
- Based on nonconservative forces, thermodynamic work depends on the path taken
from an initial state to a final state.

Conservative Forces
- When work done by the force on an object is independent of the object’s path
- Example: Gravitational, Electromagnetic, Strong, and Weak

Nonconservative Forces
- When work done by the force on an object is path-dependent
- Involves many particles and does thermodynamic work.
- Example: Friction

Key points:
• An expanding gas does positive work on its surroundings, so internal energy decreases
• A contracting gas does negative work on its surroundings, so internal energy increase.
• The work done by the surroundings on a gas is equal to the negative of the work done by the
gas on its surroundings.
• A positive work done on a system increases its internal energy, and a negative work done on a
system decreases its internal energy, assuming no heat transfer happens between the system
and its surroundings.

Formulas:
W – work(J)
1 W = Fd cos θ F – force (N)
d – displacement of the object (m)
θ – angle between the force and the displacement

2 Wby = - Won Work (Wby) done by the system on its surroundings is the
negative opposite of the work (Won )done by the
surrounding on the system (Newton’s third law)

3 W = K f - Ki
LG 5.3

First Law of Thermodynamics

Work, Heat, and Internal Energy

Since stirring water increases the speed of the molecules, does this mean water becomes hotter
when you stir it? YESSS!!!!!!
This was proven by 18th century physicist James Joule. The figure shows a
schematic diagram of James Joule’s experiment. An insulated container is
filled with water and fitted with a paddle wheel attached to a pulley
system. When the blocks of mass m are released from rest, the blocks pull
the ropes which causes the paddle wheel to turn, stirring the water. The
friction that the paddle wheels exert on the water causes the temperature
of the water to increase.

By varying the mass of the blocks, Joule found that the amount of work
that the blocks exert on the water is proportional to the increase in
water’s temperature. Later experiments showed that the constant of
proportionality is equal to 4.186 J /g · K, (specific heat of water), which is
the constant of proportionality between the heat absorbed by water and
the water’s temperature increase. This implies that if you want to increase
the temperature of 1 gram of water by 1 kelvin, you can either add 4.186 J
of heat to the water, or apply 4.186 J of work on the water. Heat and work
are equivalent in terms of increasing the temperature of a system.

In Lesson 5.1, we learned that heat transfer to or from a system changes the system’s internal energy. In
Lesson 5.2, we learned that work done on a system changes the system’s internal energy. These two
results, combined with Joule’s discovery, lead to the so-called first law of thermodynamics .

Formulas:
Quantity if positive... if negative...
ΔEint internal energy internal energy
is increasing is decreasing 1 ΔEint = Q + Won
Q heat enters the heat leaves the
system system
2 ΔEint = Q - Wby
Won for gas gas is gas is
systems contracting expanding
All units: Joules (J)
Wby for gas gas is gas is
systems expanding contracting ΔEint – internal energy
Q – heat
Won – work done on the system
Wby – work done by the system
LG 5.4

First Law
First Law of
of Thermodynamics
Thermodynamics
Thermodynamic
Thermodynamic Processes
Thermodynamic Process Processes
- The average work done by a system composed of many particles to its is mainly about
bringing the system from one state to another.
- In this sense, either heat is added/removed and or work is done by/on the system to
change its state described by its state variables, Eint(internal energy), p(pressure), V
(volume), and T (temperature).
- Isochoric, Isobaric, Isothermal, and Adiabatic.
Isochoric or Isovolumetric process Thermodynamic Characteristics
Processes
- Characterized by the heating or cooling of substances
inside a very rigid container. Isochoric Constant Volume
- In this process, any amount of heat that goes in the ΔV = 0
system will not result in volume change. Input heat
Isobaric Constant Pressure
will be converted to increase internal energy or if the Δp = 0
internal energy of the system decreases, heat will
flow out the system. Isothermal Constant Temperature
- Ideal gas undergoing isochoric process (equation 2) ΔT = 0
Isobaric process Adiabatic No heat transfer
- In an isobaric process, the system absorbs/releases Q=0
heat in the process and/or work is done by/on the
process while changing its state, thereby changing
its internal energy. Formulas:
- This is Charles’s law, which states that the volume
of an ideal gas at a constant pressure process is 1 pV = nRT (Ideal gas equation)
proportional to its Kelvin temperature (equation 3)
Isothermal process
- May be thought of to occur when a system is in
2  = = constant

constant with a heat reservoir, which is a large

enough body which can maintain its temperature
3  = = constant

even if the system absorbs heat from it. This process ΔEint = 0
4
occurs slowly, maintaining equilibrium in each step
of the process.
- For an ideal gas, the internal energy is dependent on 5 pV = nRT = constant
its temperature. Thus, the change in internal energy
of an ideal gas after an isothermal process is zero 6 Q=0
(equation 4). Boyle’s Law (equation 5)
Adiabatic process p – pressure (Pa)
V – volume (m3)
- Means that no heat will get into and out of the system. n – no. of moles
This process happens if the system is highly insulated T – temperature (K)
and/or it takes place fast enough to avoid heat to flow R – gas constant (8.314 J · mol−1 · K−1)
into or out the system. (equation 6)
 LG 5.5

First Law of Thermodynamics

First Law ofFirst Law of Thermodynamics
Thermodynamics and Processes
and Thermodynamic
Thermodynamic
Wby = pΔV ΔE = Q + W Processes
int ΔE = Q - W
on int by

Isochoric Process Isobaric Process

Recall that for an isochoric process, the volume is constant Recall that for an isobaric process, the pressure is constant
Δp = 0
ΔV = 0 Thus, the work done by the system undergoing an isobaric
Wby = pΔV process is simply
Wby = 0 Wby = pΔV
As a result, the first law of thermodynamics for an isochoric As a result, the first law of thermodynamics for an isobaric
process is reduced to: process is reduced to:
ΔEint = Q
ΔEint = Q - pΔV
Heat absorbed/released at constant volume is: Q = nCpΔT pV = nRT
ΔEint = nCV ΔT pΔV = nRΔT
Q = nCV ΔT
Substituting all the equations, we get:
Combining the last two equations: nCV ΔT = nCpΔT − nRΔT
ΔEint = nCV ΔT C p = CV + R

Isothermal Process Adiabatic Process

Recall that for an isothermal process, the temperature is Recall that in adiabatic processes, net heat flow is zero
constant Q=0
pV = nRT Therefore, the first law of thermodynamics for an adiabatic
process reduces to
ΔEint =− Wby
  p= For an ideal gas, we usually define the ratio between the heat
capacities as
γ
 =
Also, for an adiabatic process of an ideal gas,
pV γ = constant
  Wby = nRT ln
(di ko gates)
W
  by =
 LG 6.1

PV Diagrams
Workand
Work andPV
PVDiagrams
Diagrams
Pressure - Volume or PV Diagram
- A convenient way to visualize the changes in the pressure and volume of a thermodynamic system.
- Each point on a PV diagram corresponds to a different state of the system.
- Pressure (vertical axis), Volume(horizontal axis)

Key points:
• A thermodynamic system can exchange energy with its surroundings by heat transfer or by
mechanical work and in some cases by other mechanisms.
• When a system at pressure p expands from volume V 1 to V 2 , it does an amount of work that
can be calculated using the area under the curve of a PV diagram.
• If the pressure is constant during the expansion, the work is
W = p (V f − V i) constant pressure only

• A state shifting to the left on a PV diagram, the work done on the gas is positive
• A state shifting to the right on a PV diagram, the work done on the gas is negative.
• If pressure, p , times volume, V , increases, the temperature, T , and internal energy, E int, also
increase, making ΔEint positive.
• Shift to the right, ΔEint is positive – Shift to the left, ΔEint is negative

Consider a gas starting

out in the initial state at
point (pi, V i) shown in
the PV diagram

Formulas:
a 1 Wby = p (V 2 − V 1)
In an expansion from state 1 to state 2 in Figure A, the Wby = ΔV
area under the curve and the work are positive. The PV
diagram in figure A now gives us a graphical picture that, W – work (J)
indeed, the gas inside the piston does positive work done, p – pressure (Pa)
Wby , to the piston, while its volume increases. V – volume (m3)

b
2
A compression of the gas from 1 to 2 in Figure B gives a
negative area as the system’s volume decreases and the General integral form of the work done
gas does negative work, Wby, on its surroundings. by the system
c
Remember: total work (Wby) done is just
If the pressure p remains constant while the volume
changes from V 1 to V 2 (Figure C), the work done BY the the total area under the curve.
system at constant pressure is (equation 1). Figure C is the Wby = - Won
PV diagram for an isobaric process.
 LG 6.2

PV Diagrams
Thermodynamics
Thermodynamics Processes
Processes and
and PV
PV Diagram
Diagram
Isochoric Process
Notice that the area under the PV curve is zero.
Hence,
Wby = 0
ΔEint = Q - Wby

ΔEint = Q
All energy added as heat increases its internal
energy.
Vertical Line: Isochor

Isobaric Process
Is a constant-pressure thermodynamic process.
The pressure of the system does not change
during the process
The area under the curve is simply the area of a
rectangle
Wby = p (V f − V i) = pΔV

ΔEint = Q - pΔV

Horizontal Line: Isobar

Isothermal Process
The work done during the process is equal to the
area under the curve. (pero lisud icalculate daw)
Wby = nRT ln
 
Wby = p initialV initial ln
 
Curve of constant temperature: Isotherm

Idiabatic Process
When a system expands (adiabatically) – Wby is
positive and ΔEint is negative, such that internal
energy decreases. When a system is compressed
(adiabatically), Wby is negative and Eint increases.
ΔEint =− Wby
Notice how the system crosses two isotherms. This
indicates that temperature changes may occur during an Wby = (p final V − pinitial V initial)
adiabatic process, aside from changing pressure and
  final

volume of the system. W

  by =
All formulas can be found in LG 5.5 (kay medyo lisud ni
 LG 6.3

PV Diagrams
Cyclic Process
Cyclic Process
Cyclic Process
‐ The state of the system (described by pressure, volume and
ΔEint = 0
temperature of the system) at the end of the process is the same
as the state at the beginning of the process.
‐ As a result, its internal energy returns to its original value, ΔEint = Q − Wby
leaving it unchanged after the cyclic process.
‐ Work done by the system in a cyclic transformation is equal to Wby = Q (cyclic process)
the heat absorbed by the system.
Key points:
• The net work involved in a cyclic process is the area enclosed in a PV
diagram
• If the cycle goes clockwise, work done by the system, W by , is positive (e.g.
steam engine)
• If the cycle goes counterclockwise, work done by the system, W by , is
negative (e.g. refrigerator)
• In a heat engine, QH is positive but QC is negative.
• Reversible process is an equilibrium process, with the system always in
thermodynamic equilibrium.
• Heat engine is a device that transforms heat partly into work or mechanical
energy.
• Refrigerator is a heat engine operating in reverse Steam Engine

The heat flow diagram in figure 2a shows

Refrigerator the relative amounts energy transfers
through the thickness of each “pipes” or
“arrows” to and from the system. Notice
that the “pipe” from the hot reservoir is
larger compared to that going to the cold
reservoir. In fact, we can actually conclude
from the figure that
|QH| = |QC| + Wby ⇒ | QH| − |QC| = Wby

|QH| − |QC| = Q
QH + QC = Q
(wa ni tarong nga notes)