Notes:
• Heat transfer of energy due to temperature difference
• Heat flows due to thermal content
• Energy transfer until temperatures are the same (they are in
thermal equilibrium)
• Heat flows from hot object to cool one
ZERO law states that:
All objects are in thermal equilibrium with one another have same
temperature.
Thermal Equilibrium (heat stops flowing)
A B A B A B
When a hot object is placed in thermal contact with a cold object,
heat flows from the warmer to the cooler object. This continues
until they are in thermal equilibrium (the heat flow stops). At this
point, both bodies are said to have the same “temperature”.
This intuitively straightforward idea is formalized in the 0th Law of
thermodynamics and is made practical through the development of
thermometers and temperature scales.
ZERO’th LAW of Thermodynamics
If A and B are in thermal equilibrium
and B and C are in thermal equilibrium,
then A and C are in thermal equilibrium
Consequence of the zero’th law:
B acts like a thermometer, A , B and C are all at the
same “temperature”.
Operational definition of temperature (t) Need:
(1) substance
(2) property that depends on (t)
(3) reference points
(4) interpolation scheme between ref. pts.
Temperature:
• Celsius scale:
Celsius is a measurement of temperature in which 0 degrees
represents the freezing point of water, and 100 degrees
represents water’s boiling point at the standard atmosphere,
which is the mean barometric pressure at the mean sea level.
• Fahrenheit scale:
Fahrenheit is a temperature scale that bases the boiling
point of water at 212oF and the freezing point at 32oF.
Body temperature is 96oF
To Convert Between Temperatures:
𝑇𝐹 = a Tc + b
Where: a = 9/5 b = 32
Notes:
➢ absolute zero
• Temperature at which heat energy cannot be extracted
• Called zero Kelvin (0K)
• On Kelvin temperature scale no negative temp
• Increments of temp same as in Celsius
• Absolute zero is not attainable experimentally, must
extrapolated from graph
Example: Ideal Gas Thermometer with the Celsius scale.
Based on Boyle’s Law
lim ( pV͞ ) 𝑇 = 𝑐𝑛𝑠𝑡𝑎𝑛𝑡 = 𝐹 (𝑇)
𝑃 ⇾0
for fixed T depends on T
• the substance is a gas
• f (t ) is the property
• the boiling point (tb = 100C ) and freezing point (tf = 0C ) of
water are the reference points
• the interpolation is linear
ƒ(t) = lim ( 𝑝 𝑣͞ )
𝑝⇾ 0
f(t)=f(0 ͦC)(1+At)
Experimental result:
A = 0.0036609 = 1/273.15
Note:
(t = -273.15°C ) is special (t = -273.15°C) is called the absolute zero,
this suggests defining a new temperature scale (Kelvin)
T(K ) =t(C ) + 273.15
T = 0K corresponds to absolute zero (t = -273.15°C )
Better reference points used for the Kelvin scale today are
T = 0K (absolute zero) and 𝑇𝑇𝑝 = 273.16K (triple point of H2O)
Ideal Gases
Boyle’s Law and the Kelvin scale
lim ( 𝑝𝑣͞ )𝑡𝑝
lim ( 𝑝 𝑣͞ ) = ( (valid for all gases for p ⇾0)
𝑝⇾0
) 𝑇 ≡ 𝑅𝑇
𝑝⇾0 273.16
Define gas constant
An ideal gas obeys the expression pV = RT at all pressures
(⇒ the gas molecules do not interact)
lim (𝑝𝑣͞ )𝑡𝑝 𝐽
R=[ ( gas const )
𝑝→0
] = 8.31451
273.16 𝐾.𝑚𝑜𝑙
The ideal gas law :
pV = nRT p v = RT
This is an example of an equation of state
V = f (n, p,T )
𝑉
Note that : v =
𝑛
Equations of state:
IDEAL GAS LAW: pV = nRT → pV = RT
Mixture of ideal gases comprising ( ni ) moles of each
P = Pt = PA + PB + …….
𝑛𝐴 𝑅𝑇
PA = partial pressure of (A) gas
𝑉
𝑛𝐴
XA = mole fraction of (A) gas
𝑛𝑇
PA = X A *P Dalton's law
Real Gases ⇨ do not necessarily obey ideal gas law
a) Compressibility factor
𝑣͞ 𝑟𝑒𝑎𝑙
PV͞ = ZRT Z=
𝑣͞ 𝑖𝑑𝑒𝑎𝑙
High temperature Repulsions dominate Z>1 𝑣͞ 𝑟𝑒𝑎𝑙 > 𝑣͞ 𝑖𝑑𝑒𝑎𝑙
Low temperature attractions dominate Z < 1 𝑣͞ 𝑟𝑒𝑎𝑙 > 𝑣͞ 𝑖𝑑𝑒𝑎𝑙
b) Virial Expansion
Generally, neglect
𝐩𝐯͞ 𝐁(𝐓) 𝐂(𝐓)
= 𝑍(𝑇) = 1 + + + ………
𝐑𝐓 𝐯͞ 𝐯͞ 𝟐
As p⇾ 0 and v ⇾ ⇨ ideal gas B = 0 ⇨ ideal gas
(Neglect (C) and higher order
terms)
c) van der Waals Equation of state
only two parameters, derived from molecular concepts
First assume “hard sphere” molecules
PV͞ = RT becomes P (V͞ - b) RT
Now put in attraction
𝑅𝑇 𝑅𝑇 𝑎
So, P =( ) becomes P=( )−
𝑣͞ − 𝑏 𝑣͞ − 𝑏 𝑣͞ 2
𝑎
Rearranging ⇨ (𝑃 + 𝑣͞ 2 ) (𝑣͞ − 𝑏 ) = R T
Thermal expansion
Thermal expansion
• Most substances expand when heat
• One dimensional
• ∆ length (of rod) 𝛼 ∆ T
I. linear expansion
∆ L 𝛼 𝐿 ⃘ ( original length )
∆ L = 𝛼. 𝐿 ⃘ . ∆T
𝛼 : coefficient of linear expansion
its unit ⇨ o𝑐 −1
is experimentally determined
𝛼 : is positive in most materials
𝛼: is close to zero or negative in materials with very strong
atomic bonding
II. volume expansion
cutout hole become larger or smaller when heated
∆V= 𝛽. 𝑉 ⃘ . ∆T
𝛽 coefficient of volume expansion
the weak intermolecular bond cause ⇨ 𝛽 ~ 3𝛼
objects expand the same whether solid or hollow
III. Expansion of water
Water is one of the few exceptions to this behavior. When liquid
water is cooled, it contracts like one would expect until a
temperature of approximately 4 (~ 3.98) degrees Celsius is
reached. After that, it expands slightly until it reaches the
freezing point, and then when it freezes it expands by
approximately 9%
IV. area expansion
When the temperature of a surface changed ΔT, the change of
its area ΔA is very nearly proportional to its initial area
multiplied by ΔT. The Area Expansion equation is:
ΔA = γ.A0 .ΔT
Where:
a. γ : The Coefficient of Area expansion
b. A0 : Initial area of the object
c. ΔA: Area change of the object
d. ΔT: Temperature change of the object