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The Nature of Physical Chemistry and the Kinetic Theory of Gases

Chapter 1: The Nature of Physical Chemistry and the Kinetic Theory of Gases
1.1 The Nature of Physical Chemistry Macroscopics vs. Microscopics Pressure Temperature Volume Atoms Molecules Particles


Statistical thermodynamics Chemical kinetics Quantum chemistry

2 Simple Concepts from Classical Mechanics Work: or even more. if work is the applied force in the direction of motion multiplied by dl.1. .

So the work done on the spring is found to be: Harmonic oscillator . The force.Hooke’s law (For idealized spring) FIGURE 1. x. causing a departure fro the straightline condition shown. from an equilibrium position at x = 0.2 Plot of Hooke’s law for arbitrary kh. F. The force constant kh is normally constant only over short ranges and than deviates. is plotted against displacement.

Kinetic Energy(Ek) We find that the difference in kinetic energy between the initial and final states of a point body is the work performed in the process .

Potential Energy (Ep) FIGURE 1.3 ∫ Plot of Ep= - 0 Fdx = -- khx2 2 for the case of a system that obeys Hooke’s law. 1 x Conservation Laws .

. 3 Systems. Equilibrium There is no change with time in any of the system’s macroscopic properties. temperature. volume. Extensive properties (value does change with the quantity of matter) Mass. and Equilibrium Systems Open system States Closed system Isolated system Intensive properties (value does not change with the quantity of matter) Pressure.1. etc. etc. States.

.. Zeroth Law of Thermodynamics A and B are in thermal equilibrium with each other.4 Thermal Equilibrium The physiological sensations are relative and qualitative.1.. C is equilibrium with B A and C are also in thermal equilibrium with each other (Leading a way to measure temperature) Temperature is relative and qualitative ~ By Danish astronomer Olaus RΦmer Define the freezing point of water at 1 atm as 0 oC Define the boiling point of water at 1 atm as 100 oC (l − l0 ) θ= (100 0 ) (l100 − l0 ) € .

1.5 Pressure and Boyle’s Law Pressure (Force per unit area) P = ρgh € ρ: the density of the liquid g: the acceleration of gravity h: the height of the liquid ~ By an Italian physicist E. Torricelli (1 atm = 760 mm Hg height at 0 oC) Unit of pressure SI unit Non-SI unit pascal (Pa) = kg m-1 s-2 = N m-2 standard atmosphere (atm) = 101325 Pa torr (Torr) = 101325 Pa = 760 mm Hg height bar (bar) = 105 Pa .


Boyle’s Law: The pressure of a fixed amount of gas varies inversely with the volume if the temperature is maintained constant. .

15 .1.6 Gay-Lussac’s (Charles’s) Law Gay-Lussac’s Law V/T = constant (valid at constant P and n) Kelvin temperature (K) = Celsius temperature (oC) + 273.

082 atm dm3 K-1 mol-1 R = 1.8 The Equation of State for an Ideal Gas Avogadro’s Hypothesis A given volume of any gas (at a fixed temperature and pressure) must contain the same number of independent particles V ∝n (valid at constant P and T) Equation of State of an Ideal Gas PV € = nRT R= P: pressure V: volume n: number of molecules (mole = 6.314 J K-1 mol-1 (SI unit) R = 0.02 x 1023) T: temperature PV ( force /area) ⋅ volume = = force ⋅ length ⋅ K −1 ⋅ mol−1 = energy ⋅ K −1 ⋅ mol−1 nT mol ⋅ K R = 8.1.987 cal K-1 mol-1 .

PV PVm Z>1 PVm > RT repulsive force Z= = Z<1 PVm < RT attractive force nRT RT € .1.12 Real Gases The compression factor v  The gas laws hold fairly well for most gases over a “limited range of pressures and temperature”.

1 oC Critical temperature Tc v  Vapor = Gas v  T1.Condensation of gases: The critical point v  Studying the liquid-gas behavior of CO2 under pressure at varying temperatures v  The boundary between the gas and liquid regions disappeared at 31. T3: tie lines The distance between xy and yz is related to the percentage of each phase (liquid or gas) present v  A gas is compressed along isotherm T3 A --> B : PV curve fits Boyle’s law B --> C : Liquid/vapor coexist C --> D : Liquid is difficult to be compressed v  Continuity of states D --> F --> E --> A : Without having a liquid/ vapor coexist section . T2.

the tie lines become shorter until a critical point that only one phase is present Critical pressure Tc. Critical volume Vc v  The equations serve to define the critical point # ∂ 2P & # ∂P & % ( = 0 and % 2 ( = 0 $ ∂V 'Tc $ ∂V 'Tc v  There is no distinction between liquid and gas phases above the critical point Supercritical fluid Density of vapor € Density of liquid .Condensation of gases: The critical point v  At Tc.

The  van  der  Waals  Equa0on  of  State   or   .

5   x V2 .For  SO2    from  Table  1.

HW #1 Hint: .

HW #1 .

HW #1 Hint: .

HW #1 Hint: For real gas: For ideal gas: PV = Z ⋅ nRT PV = nRT .

HW #1 Hint: # ∂ 2P & # ∂P & % ( = 0 and % 2 ( = 0 $ ∂V 'Tc $ ∂V 'Tc € .