373 CH 7 and 8 Background: Properties
373 CH 7 and 8 Background: Properties
373 CH 7 and 8 Background: Properties
Properties:
Phase - a quantity of mass that is homogeneous throughout State - condition specified by phase, pressure, temperature, density, etc. Property quantitative value that depends on the state of a substance and is independent of the path to the state Intensive independent of mass, constant throughout mass (pressure, temperature, density) Extensive Varies directly to mass (mass, energy)
Units:
We will use only metric units (SI) Length(l) meter(m) Mass(m) kilogram(kg)
Volume(V) m3 , specific volume(v) = V/m Temperature Celsius (0 solid state water), Kelvin = C+273
Pure substances:
Pure substances are homogeneous, invariable chemical composition. The chemical composition is the same in all phases Examples water (H2O), ammonia (NH3), oxygen (O2) Air is considered a pure substance as long as there is no change of phase Compressible substances (or system) A substance in which changes in volume are significant (in at least one phase)
Vapor-Liquid-Solid-Phase Equilibrium Consider a piston containing water with a weight on the piston. The weight keeps the substance at constant pressure P = W/A where W weight, and A is the cross-sectional area of the piston.
As we reach saturation temperature, water is saturated liquid. Liquid water begins to turn to vapor
Temperature stays constant as liquid Is converted to vapor. When water is completely vapor, temperature Begins to rise again.
critical point
Temperature
Volume
Pressure
Temperature
Heat
Critical Point
Pressure
Temperature
Equations of state for the vapor phase of a compressible substance From chemistry, we know that for an ideal gas, Pv = RT Where v is V/n (no of moles) and R = 8.3145 kNm/kmolK
(1)
If we divide (1) by M, the molecular weight (kg/kmol): Pv /M = RT/M or: Pv = RT (3) where R is the gas constant for a particular gas and v is the specific volume Multiplying by mass (m), we get: PV = mRT (2)
(4)
TABLE B.1.4
Liquid Phase Solid Phase Critical Point
Temperature (P)
critical point
Pressure
TABLE B.1.3
Triple Point Vapor Phase
Temperature
Volume
Steam Tables, Table B.1, calculating Quality of Steam Vsatsteam = Vliquid + Vvapor mtotv = mliqvf + mvapvg Dividing by mtot, we get:
V = mliq/mtotvf + mvap/mtotvg
Let vfg = vg vf
v = vf + x vfg
Place the four states a-d listed as labelled dots in a sketch of the P-v and T-v diagrams.
P 500
T 20
v 0.001002
x Undefined
500
1400 8581
151.86
200 300
0.2
0.14302 0.01762
0.532
Undefined 0.8
3 Enthalpy
and E = q + w
The chemical energy which a system possesses is its enthalpy. Enthalpy is the change in energy at constant pressure symbol H
And H = H products H reactants
Standard enthalpy of formation is the heat absorbed when 1 mole of a substance is formed from its elements in their standard state.
The standard state of a substance is 1 mole of the substance in a specified state (solid, liquid, gas) at 1 atmosphere of pressure. The value of an enthalpy change is quoted for standard conditions: gases at 1 atm, solutions at unit concentration and substances in their normal states at a specified temperature. (usually 273K or 00C) All elements in their standard state are assigned an enthalpy of formation of 0
Standard enthalpy of reaction is the heat absorbed in a reaction at constant pressure between the number of moles of reactant shown in the equation for the reaction. Standard enthalpy of combustion is the heat absorbed when 1 mole of a substance is completely burned in oxygen at constant pressure.
Standard enthalpy of solution is the heat absorbed when 1 mole of a substance is dissolved at constant pressure in a stated amount of solvent. This may be 100g or 100ml or an infinite amount, i.e. a volume so large that on further dilution there is no further heat change.
Hr depends only on the difference between the standard enthalpy of the reactants and the standard enthalpy of the products, not on the route by which the reaction occurs.
This is Hesss Law If a reaction can proceed by more than one route the overall enthalpy is the same regardless of which route is followed.
Find the enthalpy change for the reaction CH2= CH2(g + HCl(g) C2H5Cl(g)
Given the following data
Hf = standard enthalpy change of formation Hf CH2CH2 = +52.3 KJ mol-1 Hf HCl = - 92.3 KJ mol-1 Hf C2H5Cl = -105 KJ mol-1
H = Hf products - Hf reactants
Hr = -105 (+52.3) + (-92.3) = -65KJ mol-1
Note that the formula H = Hf products - Hf reactants Applies when the data given is the enthalpy of formation. If the data given is the enthalpy of combustion the following formula is used H = Hc reactants - Hc products
It doesnt matter what the reaction is called. It may be called a combustion reaction but if the data given is the enthalpy of formation use the formula H = Hf products - Hf reactants !
Given the following enthalpies of combustion C H2(g) -394 KJ/mol -286 KJ/mol