373 CH 7 and 8 Background: Properties

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373 Ch 7 and 8 Background

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)

Force(F) Newton(N) = kg*m/s2


Energy(Q) (ability to do Work(W)) - Joule(J) = Nm Pressure(P) Pascal(Pa) = N/m2
Absolute pressure (Pabs) Gauge pressure (DP = Pabs Patm)

Volume(V) m3 , specific volume(v) = V/m Temperature Celsius (0 solid state water), Kelvin = C+273

Processes and Cycles:


Process is the path a system takes through successive states Quasi-equilibrium process process where deviation from thermodynamic equilibrium is small, and all states can be considered equilibrium states Isothermal constant temperature Isobar, Isopiestic constant pressure Isochoric constant volume Cycle process that returns to the original state (not a mechanical cycle) thermodynamic properties are returned to original values

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

Water Vapor Water Vapor Liquid Water


Heat

Temperature stays constant as liquid Is converted to vapor. When water is completely vapor, temperature Begins to rise again.

Temperature-volume diagram of a Pure substance

critical point

Temperature

Water Vapor Liquid Water

Volume

Vapor Pressure Curve of a Pure substance

Pressure

Saturation temperature Water Vapor Water Vapor Liquid Water

Temperature

Heat

Pressure-Temperature Diagram with Triple Point

Liquid Phase Solid Phase

Critical Point

Pressure

Vapor Phase Triple Point

Temperature

3-d phase diagram

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)

Steam Tables, Table B.1

TABLE B.1.4
Liquid Phase Solid Phase Critical Point

Temperature (P)

critical point

Pressure

TABLE B.1.3
Triple Point Vapor Phase

TABLES B.1.1, B.1.2 TABLE B.1.5

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 x = mvap/mtot, mliq/mtot = (1-x)


v= (1-x)vf + xvg Water Vapor mvapvg Liquid Water mliqvf

Let vfg = vg vf
v = vf + x vfg

Fill out the following table for substance water P T v x


500 500 1400 200 300 0.8 20 0.2

Place the four states a-d listed as labelled dots in a sketch of the P-v and T-v diagrams.

a) Table B.1.1 P > Psat so it is compressed liquid => Table B.1.4

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

Units SI unit = joule 1KJ = 1000J = 239.0 cal

1st law of Thermodynamics


The total energy of the universe is constant i.e energy cannot be created or destroyed but can be changed from one form to another.

Energy of a system is a state function


So E is a constant for any given change but q and w may vary (q and w are not state functions)

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

if energy is absorbed by a system H is positive if energy is released by a system H is negative

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 !

Calculate the standard enthalpy of reaction for the following


2C + 2H2(g) + O2 CH3CO2H(l)

Given the following enthalpies of combustion C H2(g) -394 KJ/mol -286 KJ/mol

CH3CO2H(l) -876 KJ/mol


r = (2x -394) + (2x-286) (-876) KJ/mol = -484 KJ/mol

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