Heat Capacity

THERMAL PROPERTIES
The heat capacity, C, of a system is the ratio of the heat added to, or
withdrawn from the system, to the resultant change in the temperature:
In this lecture we shall answer the following questions
C = q/ΔT = δq/dT [J/mol-K]
• How does a material respond to heat?
This definition is only valid in the absence of …………………
• How do we define and measure...
Usually C is given as specific heat capacity, c, per gram or per mol
- heat capacity
- coefficient of thermal expansion New state of the system is not defined by T only, need to specify or
- thermal conductivity constrain second variable:
- thermal shock resistance
- constant-volume heat capacity
• How do ceramics, metals, and polymers rank?
- constant-pressure heat capacity
cv and cp can be measured experimentally
Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/1 Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/2

Heat Capacity Vs T Theoretical Calculation of the Heat Capacity

• In 1819 Dulong and Petit found experimentally that for many solids at
• Heat capacity room temperature, cv = 3R = …………...
- increases with temperature
- reaches a limiting value of 3R
• Although cv for many elements (e.g.
Heat capacity, Cv
lead and copper) at room temp. are
3R Cv= constant indeed close to 3R, cv values of
silicon and diamond are significantly
gas constant lower than 25J/K.mol.
= 8.31 J/mol-K
• Low temp. measurements showed a
Adapted from Fig. 19.2,
Callister 6e. strong temperature dependence of cv.
θD T (K) Actually, cv 0 as T 0 K.
Debye temperature
(usually less than Troom) Figure 6.1: Gaskell 3rd ed.
• Atomic view: Calculation of heat capacity of solids, as a f(T), was one of the early
- Energy is stored as atomic vibrations. driving forces of the quantum theory. The first explanation was
- As T goes up, so does the avg. energy of atomic vibration. proposed by ………… in 1906.
Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/3 Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/4
 Theoretical Calculation of the Heat Capacity Heat Capacity: Comparison
• Although Einstein's treatment
agrees with the trend of the material cp (J/kg-K)
experimental values, it was not exact. • Polymers at room T
Polypropylene 1925 cp: (J/kg-K) Specific Heat
• Einstein formula predicts faster Polyethylene 1850 Cp: (J/mol-K)
decrease of cv as compared with Polystyrene 1170
experimental data. Teflon 1050
• Why is cp significantly
• This discrepancy is caused by the • Ceramics
larger for polymers?
Magnesia (MgO) 940

increasing cp
fact that the oscillators do not vibrate
with a single frequency. Alumina (Al2O3) 775
Glass 840
• Metals
Figure 6.2: Gaskell 3rd ed.
Aluminum 900
cv

Debye enhanced the model by treating the Steel 486

quantum oscillators as collective modes in the Tungsten 128 Selected values from Table 19.1, Callister 6e.

solid - phonons. And by considering that the Gold 138

oscillators vibrate with a range of frequencies.
Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/5 Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/6

Properties From Bonding: α Thermal Expansion

• Coefficient of thermal expansion, α • Materials change size when heating.
length, Lo L final − L initial Tinit
= α(Tfinal − Tinitial ) Linit
unheated, T 1 coeff. thermal expansion L initial
ΔL Tfinal
Lfinal
ΔL coefficient of
heated, T 2 = α (T2-T1) thermal expansion (1/K)
Lo
• Atomic view: Mean bond length increases with T.
Energy Bond energy
r(T1)
r(T5)
Adapted from Fig. 19.3(a), Callister 6e.

ro Bond length (r)

α is larger if Eo is smaller.
increasing T

r
T5
larger α bond energy vs bond length
curve is “asymmetric”
smaller α T1

Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/7 Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/8
 Thermal Expansion: Comparison Thermal Conductivity

Material α (10-6/K) • General: The ability of a material to transfer heat.

• Polymers at room T • Quantitative:
Polypropylene 145-180 temperature
Polyethylene 106-198 dT
90-150
q = −k gradient
Polystyrene heat flux dx
Teflon 126-216 (J/m2-s)
• Metals thermal conductivity (J/m-K-s)
• Q: Why does α
increasing α

Aluminum 23.6
Steel 12 generally decrease
Tungsten 4.5 with increasing T1 T2 > T 1
Gold 14.2 bond energy? x1 heat flux x2
• Ceramics
Magnesia (MgO) 13.5
Alumina (Al2O3) 7.6
Soda-lime glass 9 Selected values from Table 19.1, Callister 6e. • Atomic view: Atomic vibrations in hotter region carry
Silica (cryst. SiO2) 0.4 energy (vibrations) to cooler regions.

Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/9 Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/10

Thermal Conductivity: Comparison Example: Thermal Stress

• Occurs due to:
Material k (W/m-K) Energy Transfer - uneven heating/cooling
• Metals - mismatch in thermal expansion.
Aluminum 247 By vibration of
Steel 52 atoms and • Example:
Tungsten 178 motion of - A brass rod is stress-free at room temperature (20°C).
Gold 315 electrons - It is heated up, but prevented from lengthening.
• Ceramics
increasing k

- At what T does the stress reach 172MPa (compression)?

Magnesia (MgO) 38
Alumina (Al2O3) 39 By vibration of Troom
Soda-lime glass 1.7 atoms
Lroom ΔL ΔL
Silica (cryst. SiO2) 1.4 = ε thermal = α(T − Troom )
T
• Polymers L room
Polypropylene 0.12 By vibration/
Polyethylene 0.46-0.50 rotation of chain
Polystyrene 0.13 molecules compressive σ keeps Δ L = 0
Teflon 0.25
Selected values from Table 19.1, Callister 6e.
Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/11 Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/12
 Thermal Shock Resistance Space Shuttle Thermal Protection System
Re-entry T
• Occurs due to uneven heating/cooling. Fig. 19.2W, Callister 6e.
Distribution • Materials developed
• Example: Assume top thin layer is rapidly cooled from T1 to T2: previously by the aerospace
Is there a single
industry are ………….. for the
rapid quench material which
shuttle
satisfies all these
σ requirements? • They are too dense or non-
tries to contract during cooling T 2 Tension develops at surface reusable
reinf C-C silica tiles nylon felt, silicon rubber
doesn’t want to contract T1 σ = −Eα(T1 − T2 ) (1650°C) (400-1260°C) coating (400°C)

1. Maintain the temperature on the inner airframe below certain temp. [eg., 175°C] for a
Temperature difference that Critical temperature difference maximum outer surface temperature of 1465°C.
can be produced by cooling: for fracture (set σ = σf) 2. Remain usable for 100 missions, with a maximum turnaround time of 160 h.
quench rate σf
(T1 − T2 ) = (T1 − T2 ) fracture = 3. Provide and maintain an aerodynamically smooth outer surface.
k Eα 4. Be constructed of low-density materials.
5. Withstand temperature extremes between -110°C and 1465°C.
set equal 6. Be resistant to severe thermal gradients and rapid temperature changes.
σk 7. Be able to withstand stresses and vibrations that are experienced during launch, as
• Result: (quench rate ) for fracture ∝ f well as thermally induced stresses imposed during temperature changes.
Eα
σf k 8. Experience a minimum absorption of moisture and other contaminants during
• Large thermal shock resistance when is large. storage between missions.
Eα 9. Be made to adhere to the airframe that is constructed of an aluminum alloy.
Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/13 Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/14

Space Shuttle Thermal Protection System

• For regions that are exposed to higher
temperature (400 to 1260°C);
• ceramic tiles (more complex) are used
• because ceramics are thermal insulators
and can withstand high temperature.
• 24,300 tiles (70% or the exterior area)
• each tile is different
FIGURE 23.17 Photograph showing the
installation of thermal protection ceramic
750X
tiles on the Space Shuttle Orbiter.
SEM micrograph of a Space Shuttle Orbiter
ceramic tile showing silica fibers after sintering
Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/15
Summary
A material responds to heat by:
increased vibrational energy
redistribution of this energy to achieve thermal equilibrium.
Heat capacity:
energy required to increase a unit mass by a unit temp.
polymers have the ……. values.
Coefficient of thermal expansion:
the stress-free strain induced by heating by a unit T.
polymers have the ……… values.
Thermal conductivity:
the ability of a material to transfer heat.
metals have the ……… values.
Thermal shock resistance:
the ability of a material to be rapidly cooled and not crack.
Maximize σfk/Eα.
Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/16
 Next time:

Magnetic Properties

Dr. M. Medraj Mech. Eng. Dept. - Concordia University MECH 221 lecture 22/17