(Cont'd) Review of Baisc Concepts
(Cont'd) Review of Baisc Concepts
(Cont'd) Review of Baisc Concepts
Office: EA-05-15
E-mail: mpeshin@nus.edu.sg
Aug 15, 2023
1
(Review) Mathematical Test of a Property as a continuous
function
(1) A property satisfies continuum requirement and from math,
𝑧 𝑥 𝑦
𝜕𝑧 𝜕𝑧
𝑑𝑧 = 𝑑𝑥 + 𝑑𝑦
𝜕𝑥 ! 𝜕𝑦 "
𝑃𝑉 = 𝑛𝑅𝑇 𝑃𝑣 = 𝑅𝑇
𝑇 = 𝑃 𝑣⁄𝑅 Experimental fact
• A property is independent of path. The change from points “A” to “B” can be
obtained by a partial integration of any path to obtain the total change on a surface.
(e.g. path “C” or the sum of dotted paths).
2
Mathematical Test of a Property as a continuous function
(2) From mathematics, for a continuous function of the form z=z(x,y), the order of
partials of z with respect to x and y would be immaterial:
𝜕 𝜕𝑧 𝜕 𝜕𝑧
=
𝜕𝑦 𝜕𝑥 ! " 𝜕𝑥 𝜕𝑦 " !
Order of differentiation is immaterial.
𝜕 𝜕𝑇 𝜕 𝜕𝑇
=
𝜕𝑣 𝜕𝑃 # $ 𝜕𝑃 𝜕𝑣 $ #
• For ideal gas, the equation of state is Pv=RT, obtaining the second order differentials:
𝜕 𝜕𝑇 𝜕 𝑣 1 𝜕 𝜕𝑇 𝜕 𝑃 1
= = = =
𝜕𝑣 𝜕𝑃 # $ 𝜕𝑣 𝑅 𝑅 𝜕𝑃 𝜕𝑣 $ # 𝜕𝑃 𝑅 𝑅
$ #
3
Mathematical Test of a Property as an independent parameter
𝜕𝑧 𝜕𝑧 𝜕𝑦 𝜕𝑥 1
= =
𝜕𝑥 % 𝜕𝑦 %
𝜕𝑥 % 𝜕𝑧 ! 𝜕𝑧
𝜕𝑥 !
𝜕𝑇 𝜕𝑇
𝑑T = 𝑑P + 𝑑𝑣
𝜕𝑃 # 𝜕𝑣 $
• If we now take the partial derivative of each term with respect to P at constant T:
𝑑𝑇 𝜕𝑇 𝜕𝑃 𝜕𝑇 𝜕𝑣
= +
𝑑𝑃 & 𝜕𝑃 # 𝜕𝑃 & 𝜕𝑣 $ 𝜕𝑃 &
𝜕𝑇 𝜕𝑇 𝜕𝑣
0 = 1 +
𝜕𝑃 # 𝜕𝑣 $ 𝜕𝑃 & 4
Mathematical Test of a Property as an independent parameter
𝜕𝑇 𝜕𝑇 𝜕𝑣
0= 1+
𝜕𝑃 # 𝜕𝑣 $ 𝜕𝑃 &
𝜕𝑇 𝜕𝑣
𝜕𝑣 $ 𝜕𝑃 &4
0=1+ 𝜕𝑇
𝜕𝑃 #
𝜕𝑃 𝜕𝑇 𝜕𝑣
0=1+
𝜕𝑇 # 𝜕𝑣 $ 𝜕𝑃 &
𝜕𝑃 𝜕𝑇 𝜕𝑣
−1 = constant
𝜕𝑇 # 𝜕𝑣 $ 𝜕𝑃 &
5
Example 1-1
Note the definitions of the expansion (β) and compression (κ) coefficients for
real gases are respectively given by:
6
(Cont’d) Example 1-1
• Consider the relationship between V, T and P of a gas contained in a vessel (closed
system). The experimental relationship between the expansion and compression
coefficients of the gas are inversely proportional to T and P, respectively. Derive
PV/T=constant.
• Solution:
𝑉=𝑉 𝑃 𝑇
From mathematics, the total differential of V is given by
𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑇 + 𝑑𝑃
𝜕𝑇 $ 𝜕𝑃 &
Using the definitions and the experimental relation of the gas, the above can be re-
written as
𝑑𝑇 𝑑𝑃
𝑑𝑉 = 𝛽𝑉𝑑𝑇 − 𝜅𝑉𝑑𝑃 = 𝑉 −𝑉
𝑇 𝑃
7
(Cont’d) Example 1-1
• Consider the relationship between V, T and P of a gas contained in a vessel (closed
system). The experimental relationship between the expansion and compression
coefficients of the gas are inversely proportional to T and P, respectively. Derive
PV/T=constant.
• Solution:
𝑑𝑇 𝑑𝑃
𝑑𝑉 = 𝛽𝑉𝑑𝑇 − 𝜅𝑉𝑑𝑃 = 𝑉 −𝑉
𝑇 𝑃
𝑑𝑉 𝑑𝑇 𝑑𝑃
− + =0
𝑉 𝑇 𝑃
Integrating, we have,
ln 𝑉 − ln 𝑇 + ln 𝑃 = c c: constant
𝑃𝑉
= 𝑒' : constant
𝑇
8
Example 1-2
• Estimate the change in the specific volume of air (assuming ideal gas)
if the temperature and pressure changes are from T1= 25 oC and P1=
122 kPa to T2= 65 oC and P2= 102 kPa, respectively. Compare the
changes as calculated directly from the ideal gas law (as derived in
example 1-1).
• Solution:
𝑃𝑉 = 𝑚𝑅𝑇 (𝑣 = 𝑉 ⁄𝑚)
𝑃𝑣 = 𝑅𝑇
𝑘𝐽
𝑅𝑇 𝑅! 8.3145 (𝑘𝑚𝑜𝑙. 𝐾) 𝑘𝐽
𝑣= 𝑅=
𝑀
=
𝑘𝑔
= 0.287 (
𝑘𝑔. 𝐾
) M: average molar mass of air
𝑃 28.98 (
𝑘𝑚𝑜𝑙
)
𝜕𝑣 𝜕𝑣 𝑅 𝑅𝑇
𝑑𝑣 = 𝑑𝑇 + 𝑑𝑃 = 𝑑𝑇 + − ( 𝑑𝑃
𝜕𝑇 $ 𝜕𝑃 & 𝑃 𝑃
𝑑𝑣 = 0.248 m) /kg
9
The Zeroth Law of Thermodynamics
• When a body is brought into contact with another body that is at a different
temperature, heat is transferred from the body at higher temperature to the one at
lower temperature until both bodies attain the same temperature.
• At that point, the heat transfer stops, and the two bodies are said to have reached
thermal equilibrium.
• The zeroth law of thermodynamics states that if two bodies are in thermal
equilibrium with a third body, they are also in thermal equilibrium with each other.
10
Temperature Scales
• All temperature scales are based on some easily reproducible states such as the
freezing and boiling points of water, which are also called the ice point and the
steam point, respectively.
• Kelvin scale
• Rankine scale
11
Ideal-Gas Temperature Scale
• A temperature scale that turns out to be nearly identical to the Kelvin scale is the
ideal-gas temperature scale.
• This thermometer is based on the principle that at low pressures, the temperature of
a gas of fixed volume varies linearly with pressure at sufficiently low pressures.
𝑇 = 𝑎 + 𝑏𝑃
12
Constant-Volume Gas Thermometer
14
How are the numerical numbers of an absolute
temperature scale assigned?
1) The number of divisions between steam point and
ice point:
𝜃* − 𝜃+ = 100 or 180
Empirical temperature
𝜃* 𝑃*
= ≈ 1.3661
𝜃+ 𝑃+
Solving,
100 100
𝜃+ = = = 273.15 [K] Kelvin scale
𝑃* 0.3661
𝑃+ − 1
180 180 Rankin scale
𝜃+ = = = 491.69 [R]
𝑃* 0.3661
−1 15
𝑃+
How are the numerical numbers of an absolute
temperature scale assigned?
16
Example 1-3
• Solution:
17
Example 1-4
18
(Cont’d) Example 1-4
• The volume of mercury contained in a bulb type thermometer is Vb,0 (m3) at ice
point. If the capillary of thermometer has a cross sectional area As,0 (m2) and the
linear and volumetric expansion coefficients of glass and mercury are αg(1/K) and
βm(1/K) respectively, determine the change in height of mercury column for a
small change in temperature, ΔT(K)?
• Solution:
≈ 𝐴0,/ 1 + 2𝛼1 𝛥𝑇
19
(Cont’d) Example 1-4
• The volume of mercury contained in a bulb type thermometer is Vb,0 (m3) at ice
point. If the capillary of thermometer has a cross sectional area As,0 (m2) and the
linear and volumetric expansion coefficients of glass and mercury are αg(1/K) and
βm(1/K) respectively, determine the change in height of mercury column for a
small change in temperature, ΔT(K)?
• Solution:
20
(Cont’d) Example 1-4
• The volume of mercury contained in a bulb type thermometer is Vb,0 (m3) at ice
point. If the capillary of thermometer has a cross sectional area As,0 (m2) and the
linear and volumetric expansion coefficients of glass and mercury are αg(1/K) and
βm(1/K) respectively, determine the change in height of mercury column for a
small change in temperature, ΔT(K)?
• Solution:
𝑉2 = 𝑉- + 𝑉* = 𝑉- + 𝐴* ℎ
𝑉-,/ 𝛽2 − 3𝛼1
ℎ= 𝛥𝑇
𝐴*,/ 1 + 2𝛼1 𝛥𝑇
21
Types of Temperature Measuring Devices
𝜃( 𝑋( q = empirical temperature
=
𝜃3 𝑋3 X = thermometric property
22
Properties of Pure Substances
23
What is a pure substance?
24
Phases of a pure substance
• Ex) At room temperature and pressure, copper is a solid, mercury is a liquid, and
nitrogen is a gas.
• A substance may have several phase within a principal phase, each with a different
molecular structure. (e.g. carbon – graphite or diamond)
25
Phase-change processes
• There are many practical situations where two phases of a pure substance coexist in
equilibrium. Water exists as a mixture of liquid and vapor in the boiler and the
condenser of a steam power plant. The refrigerant turns from liquid to vapor in the
freezer of a refrigerator.
• When the temperature keeps rising until it reaches 100 oC, water is still a liquid, but
any heat addition will cause some of the liquid to vaporize. A liquid that is about to
vaporize is called a saturated liquid.
26
Phase-change processes
1) Compressed Liquid and Saturated Liquid
27
(Cont’d) Phase-change processes
28
(Cont’d) Phase-change processes
2) Saturated Vapor and Superheated Vapor
• As we continue transferring heat, the vaporization process continues until the last
drop of liquid is vaporized.
• At state 4, the entire cylinder is filled with vapor that is on the borderline of the
liquid phase. Any heat loss from this vapor will cause some of the vapor to condense
(phase change from vapor to liquid). A vapor that is about to condense is called a
saturated vapor.
29
(Cont’d) Phase-change processes
30
Saturation Temperature and Saturation Pressure
31
Latent heat
• It takes a large amount of energy to melt a solid or vaporize a liquid. The amount of
energy absorbed or released during a phase-change process is called the latent heat.
Energy absorbed
Energy release
Liquid
Vapor
32
Cooling leafy vegetables – vacuum cooling
33
T-v Diagram
• As the pressure is increased, the saturation line continues to shrink, and it becomes
a point when the pressure reaches 22.06 MPa for the case of water.
• This point is called the critical point, and it is defined as the point at which the
saturated liquid and saturated vapor states are identical.
34
T-v Diagram
Single phase
Single phase
Two phases
35
P-v diagram
• The general shape of the P-v diagram of a pure substance is very much like the T-v
diagram, but the T=constant lines on this diagram have a downward trend.
36
Extending the Diagrams to Include the Solid Phase
• Most substances contract during a solidification (i.e., freezing) process. Others, like
water, expand as they freeze.
37
P-T diagram
• The P-T diagram is often called the phase diagram.
• The sublimation line separates the solid and vapor regions, the vaporization line
separates the liquid and vapor regions, and the melting line separates the solid and
liquid regions.
• These three lines meet at the triple point, where all three phases coexist in
equilibrium.
38
P-v-T surface
39
Property tables
• For most substances, the relationships among thermodynamic properties are too
complex to be expressed by simple equations. Therefore, properties are frequently
presented in the form of tables.
• For example, the Tables by Rogers and Mayhew is a table for undergraduates, and
one should be familiar with the units, nomenclature, etc., found in the tables. Some
of the common terminologies used are:
1) “f” refers to saturated liquid, e.g., uf is the internal energy per kg of water at
saturated conditions.
2) “g” refers to saturated vapour, e.g., hg is the enthalpy at dry saturated vapour
conditions.
3) “i” refers to saturated solid, e.g., for water, it would be ice at saturated conditions.
4) “fg” refers to the difference between the vapour to liquid properties at saturated
conditions, e.g., sfg=sg-sf at saturated conditions.
5) “u” refers to the internal energy per kg of the substance.
6) “h” refers to the enthalpy (h=u+Pv).
7) “s” refers to the entropy (ds=dq/T).
40
Enthalpy – a combination property
• In the analysis of certain types of processes, particularly in power generation and
refrigeration, we often encounter the combination of properties u + Pv, defined as a
new property, enthalpy.
ℎ = 𝑢 + 𝑃𝑣 (kJ/kg)
𝐻 = 𝑈 + 𝑃𝑉 (kJ)
• The internal energy is frequently not listed in tables, but it can be always be
determined from u=h-Pv.
41
Saturated liquid and saturated vapor states
Example 2-1
• A rigid tank contains 50 kg of saturated liquid water at 90 oC.
Determine the pressure in the tank and the volume of the tank.
Solution:
𝑉 = 𝑚𝑣 = 50 0.001036 = 0.0518 m3
42
Saturated liquid-vapor mixture
• During a vaporization process, a substance exists as part liquid and part vapor. To
analyze this mixture properly, we need to know the propertions of the liquid and
vapor phases in the mixture.
• We define a new property called the quality x as the ratio of the mass of vapor to
the total mass of the mixture:
𝑚#%9:; 𝑚1
𝑥= =
𝑚4:4%< 𝑚8 + 𝑚1
𝑚<+=>+? 𝑚8
1−𝑥 = =
𝑚4:4%< 𝑚8 + 𝑚1
43
(Cont’d) Saturated liquid-vapor mixture
• For the two-phase mixtures, the volume occupied by mixtures is the sum of the
liquid and gaseous volumes.
𝑉 = 𝑉8 + 𝑉1
𝑉 = 𝑚8 𝑣8 + 𝑚1 𝑣1
𝑉 𝑚8 𝑚1
=𝑣= 𝑣8 + 𝑣
𝑚4:4%< 𝑚4:4%< 𝑚4:4%< 1
Volume of liquid Volume of gas
𝑣 = 1 − 𝑥 𝑣8 + 𝑥𝑣1
𝑣 = 𝑣8 + 𝑥 𝑣1 − 𝑣8
𝑣 − 𝑣8 𝑣
Thus, 𝑥= ≈ 𝑣! << 𝑣
𝑣81 𝑣81
The same approximation cannot be applied to the other properties
such as internal energy, enthalpy or entropy. 44
(Cont’d) Saturated liquid-vapor mixture
𝑣 = 1 − 𝑥 𝑣8 + 𝑥𝑣1 = 𝑣8 + 𝑥𝑣81
• Using the linear rule, the quality (x), can also be obtained from other given values
of u, or h, or s, e.g.,
𝑠 − 𝑠8 ℎ − ℎ8 𝑢 − 𝑢8
𝑥= = =
𝑠81 ℎ81 𝑢81
45
(Cont’d) Example 2-2
• Find the states of water-steam mixture for the following given conditions:
Solutions:
34
P=0.8 bar
100
93.5
2.087
• Look up the Table where column 1 is the saturated pressure, and at 0.8 bar, the corresponding
temperature is only 93.5 oC.
• This temperature is found to be less than 100 oC (given), thus, we conclude that the steam is
super-heated (that is, temperature of state higher than the saturated temperature).
47
(Cont’d) Example 2-2
(c) At P=2.7 bar, x=0.5,
vg=0.6686 m3/kg
• Interpolate for v at pressure (P) when values of v1 and v2 are available from the
Tables at P1 and P2.
T P2 v2
T P v
𝑃( − 𝑃3 𝑃 − 𝑃3
=
𝑣( − 𝑣3 𝑣 − 𝑣3
𝑃 − 𝑃3
𝑣 = 𝑣3 + 𝑣( − 𝑣3
𝑃( − 𝑃3
v2 v v1
49
Example 2-3
• Find the specific volume of steam for P=2.5 MPa, and T=275 oC.
Solutions:
P=25 bar
275
223.9
superheated
50
(Cont’d) Example 2-3
• Find the specific volume of steam for P=2.5 MPa, and T=275 oC.
Solutions: