CHE317 Final Vocabulary

if system A is in thermal equilibrium with system B and system B is in thermal equilibrium with system C, then system A is in thermal equilibrium with system C

energy may not be greater nor destroyed, only transferred or changes from one form to another

∆U = q + w, where U is a state function

one cannot convert heat into work in a cyclic process without losing some heat to a low temperature reservoir

(dS)↓U,V >/= 0; (dA)↓T,V </= 0

the entropy of all pure perfect crystalline substances is zero at zero kelvin

P = (nRT/V-nb)-(n^2a/V^2) = (RT/Vm-b)-(a/Vm^2)

P = (nRT/V-nB)-(n^2a/V(√T)(V+nB)) = (RT/Vm-B)-(A/Vm(√T)(Vm+B)

temperature at which a gas behaves most ideally

Tb = (a/bR)

any property that can be determined by thermodynamic properties alone

thermodynamic properties that are not affected by the size of the system

thermodynamic properties that are affected by the size of the system

energy and matter can be transferred from system to surroundings and vice versa

energy, but not matter, may be transferred

neither energy nor matter may be transferred

process that occurs in an isolated system, no conduction or transmission of heat

a process that may be reversed at any moment by changing an independent variable by an infinitesimal amount

delta U

a state function, the sum of heat and work

(of a carnot engine) is the ratio of the net work obtained (-w) to the fuel burned to provide heat (qz)

H=U + PV

delta H

total heat content of a system, equal to the internal energy of the system plus the product of pressure and volume

Cp(T) --> T³ as T-->0

dS = (dqrev/T)

the measure of a system's thermal energy per unit temperature that is unavailable for doing useful work

G=H-TS

A=U-TS

Cvm = 3/2R, Cpm = 5/2R

Cvm = 5/2R, Cpm = 7/2R

a=e^(µ-µ⁰/RT)

molar free energy

when all three phases are in equilibrium at a particular point

δ/δT(∆G/T)p = (-∆H/T²)

(dP/dT) = (∆Hm/T∆Vm)

ln(P2/P1) = (-∆vapH/R)(1/T2-1/T1)

ln(K2/K1)=(-∆rxnH°/R)(1/T2-1/T1)

the derivative of the temperature with respect to the pressure at constant enthalpy

the temperature at which uj-t = 0

the temperature, for a gas, above which it is impossible to liquify, regardless of pressure

the assumption that different gases have the same equation of state if each gas is described by reduced variables

the vapor pressure of component A as Xa --> 0 is linear in Xa but the slope is not equal to Pa*

solutions which exhibit positive deviations from Raoult's Law

solutions which exhibit negative deviations from Raoult's Law

the rates of chemical reactions = active masses of reacting species

the sum of exponents in the rate law; tells how many species are coming together at the critical time in the reaction

the amount of time required for half of the initial concentration of the reactant to react

a species that speeds up a reaction, without being consumed itself, by lowering the activation energy

chemical species found at the top of the activation barrier. it is an energy maximum in the direction of the reaction pathway, but an energy minimum in all other dimensions

Ea

chemical species which lies somewhere along the reaction pathway and is a local energy minimum. However, such a species may or may not be able to isolated depending on the depth of its energy well

(d[I]/dt) = 0

the concentration of the intermediate does not appreciably change with time

lnK = lnA-(Ea/RT) or K = Ae^(-Ea/RT)

half-life is direction proportional to initial concentration concentration versus time is linear

[A] = -akt + [A₀]

t1/2 = [A₀]/2ak

natural log of concentration versus time is linear half life is constant

ln[A] = -akt + ln[A₀]

t1/2 = ln2/ak

reciprocal concentration versus time is linear half life doubles

1/[A] = akt + 1/[A₀]

t1/2 = 1/ak[A₀]

lord kelvin

rediscovered Carnot's work, corrected it to conform with the first law of thermodynamics

worked with Thomson to correct Carnot's work to conform with the first law of thermodynamics

french engineer who most likely would have discovered the first and second laws of thermodynamics had he not died of cholera at age 36

proved heat is a method by which system exchange energy, showed that the same change in state (a certain rise in temperature) can be accomplished either by doing work on a body or heating it

a Dutch chemist who was the first to show that for non-metallic solids, Cp(T) --> T3 as T-->0, this T3 temperature dependence has been shown to be valid experimentally

first postulated the third law of thermodynamics

first postulated that the entropy of any reaction approaches zero as the temperature approaches 0 Kelvin

Pi = XiPi*

a = P/Po, a = f/Po

states that the entropy of vaporization is almost the same value, about 85-88J, for various kinds of liquids at their boiling point

1. to products

2. to reactants

3. to side with fewer molecules

4. to side with more molecules

5. to side with more molecules

6. to side with fewer molecules

Tr = T/Tc

Pr = P/Pc

Vr = V/Vc

path independence means that the enthalpy change for any sequence of reactions that sum to the same overall reaction is identical

addresses the intermolecular forces the coefficient of thermal expansion related to the attractive forces between molecule Constant in that takes into account the attractive forces for a pure substance

addresses the actual volume of the gas particles related to the repulsive forces between molecules A constant that takes into account the repulsive forces for a pure substance, minimum

two moles of an ideal monatomic gas expand adiabatically into an evacuated container (vacuum), tripling the original volume this type of expansion is a

using the excess of everything except one reactant

Swedish chemist who proposed molecular definitions of acids and bases

thermodynamic process in which the temperature of the system remains constant

a process occurring at constant pressure

thermodynamic process taking place at constant volume

intensive property state function a measure of the average kinetic energy of the particles that make up a substance

energy transferred due to a temperature difference extensive property not a state function the energy of the random motion of the particles that make up a substance

the energy transferred by virtue of a mechanical link between systems dw=-PdV for a compression, reversible work (on system) is minimum work for an expansion, reversible work (by system) is maximum work

the rate at which the internal energy changes with volume at constant temperature

a method of expansion in which a gas or liquid at pressure P1, without a considerable change in kinetic energy, flows into a region of lower pressure P2

the temperature at which the vapor starts to condense

the temperature at which the liquid starts to vaporize

British chemist and physicist known for his invention of the vacuum flask which he used in conjunction with research into the liquefaction of gases

German scientist, engineer, and businessman who discovered a refrigeration cycle and invented the first industrial-scale air separation and gas liquefaction processes, which lead to the first reliable and efficient compressed-ammonia refrigerator in 1876