Thermodynamics/The First Law Of Thermodynamics
Thermodynamics = study of the transformation of E. from one form to another, and from one system to another.
Thermal energy = E. associated with motion of atoms and molecules in a substance.
Thermodynamic systems 
• System = definite quantity of mass bounded by a real or imaginary closed surface.
• Surrounding = any systems that can interchange E. with a given system.
• A system exchange E. with surroundings by doing mechanical work or by heat flow.
• If no E. interchange takes place, then the system is isolated.
Thermodynamic coordinates (state variables) 
They are the values that determine the state of a system (e.g. P, T and density).
Gross quantities of the system, measured by lab operations. (e.g. P, V, T, m).
Quantities that describe the atoms and molecules of the system and their properties (e.g. m and v of molecules).
Process = change in the thermodynamics coordinates.
Process in which the system is always in equilibrium with its surrounding.
Process in which the system is not in equilibrium with its surroundings.
Occurs when the change in thermodynamic coordinates is large and sudden.
Equation of state 
- It is a relation between P, V and T of a substance.
- It exists for every homogenous substance.
- E.g. P may be considered as a function of V and T: P = f (V,T).
- A perfect gas is one in which intermolecular forces are considered negligible.
Common forms of the equation of state of an ideal gas: PV = nRuT PV = mRT where n is the number of moles, Ru is the universal gas constant, and R is the specific gas constant. The universal and specific gas constants are related as follows: R=Ru/M, where M is the molecular weight of the gas. Using this relation and the fact that n=m/M, the two equations above can be derived from each other. The value of the universal gas constant is: Ru=8314J/(kg*mole*K)=4.97*10^4(ft*lb)/(slug*mole*R) Note: Some textbooks do a poor job of specifying whether to use the universal or specific gas constant. Remember that if the equation contains mass (or density) use the specific gas constant. If the equation contains the number of moles, use the universal gas constant. If you still aren't certain, make sure the units check out.
- State function = function that depends only on the state of the system and does not vary as long as the system has definite and fixed state variables.
Mechanical work 
Consider a gas in a cylindrical piston. F = p A ---> dW = F dx = p A dx = p dV ---> W = ∫ p dV (= area under p–V curve).
Work done by the gas
The gas expands.
Work is +ve.
Work done on the gas
The gas contracts.
Work is –ve.
Work and heat depend on path 
- From initial state a to final state c, a system may take path
o a b c, doing greatest work.
o a d c, doing minimal work.
o a c, doing intermediate work.
- Work thus depends not only on final and initial states but also on intermediate ones. Work is thus not a property of a system.
- Same result follows by computing flow of heat during the process. Thus, both work and heat depend on path and neither can be conserved alone.
o Work = E. transmitted from one system to another so that a difference in T is not directly involved.
o Values of specific heat depend on conditions:
At constant volume (isometric)
Qv = n cv ∆T
cv = molar specific heat at constant V
At constant pressure (isobaric)
Qp = n cp ∆T
cp = molar specific heat at constant P
cp = cv + R , Qv = Qp, but ∆T = ∆T.
The First Law of Thermodynamics 
- “When heat is transformed into any other form of E. the total amount of E. remains constant for an isolated system.”
- Because the same change in internal E. can be obtained by adding heat, or having work done on the system or by a combination of these process, the internal E. change is independent of how the change was achieved.
- Initial and final internal E. depend only on changes in T, P and V.
- If an amount of heat Q is supplied to a system, it expands and does an amount of work W. Change in internal E. (∆U) is given by:
∆U = Uf – Ui = Q - W
Where Ui and Uf = initial and final values of the internal E. If ∆U > 0, internal E. is increased. If ∆U < 0, it is decreased.
- The first rule of thermodynamics gives a mean to determine changes in internal E., but not the absolute value of the internal E.
- The following sign rules must be used:
Applications of the First Law of Thermodynamics 
1) Isometric process:
- It occurs at constant V. Thus, W = 0.
- From the 1st rule of thermodynamics,
∆U = Qv = n cv ∆T
- Quantity of heat supplied to a system at constant V is thus equal to the increase in the internal E. of the system.
2) Isobaric process:
- It occurs at constant P. e.g. water boiled and vaporized in a steam engine.
- W = ∫ P dV = P ∫ dV = P (Vf – Vi) ; Q = m Lv.
- From the 1st rule of thermodynamics,
∆U = m Lv – p (Vf – Vi)
Where Vf = volume of vapor, Vi = volume of liquid.
3) Cyclic process:
- In which final state and initial state are the same. Since internal E. is a state function, internal E. doesn’t change during cyclic process. Thus, ∆U = 0.
- From the 1st rule of thermodynamics,
Q = W
- Thus, in a cyclic process, the amount of heat gained or lost through the cycle is equal to the amount of work done = area enclosed by the cycle.
4) Isothermal process:
- It occurs at constant T. e.g. in thermostats. Thus dT = 0.
- P = n R T / V ---> WT = ∫ (n R T / V) dV = n R T ln (Vf / Vi).
- Since T is constant, Pi Vi = Pf Vf
- (Vf / Vi) = (pi / pf).
WT = n R T ln (Vf / Vi) = n R T ln (pi / pf)
5) Adiabatic process :
- It occurs so that no heat flows into or out of the system. E.g. by sealing the system off from its surroundings with insulating material or by performing the process quickly (because flow of heat is slow). Thus Q = 0.
- From 1st rule of thermodynamics,
∆U = Uf – Ui = – W
- Thus, if work is done on the system, internal E. increases by exactly the amount of work done on the system.
- If work is done by the system (gas expand), internal E. decreases by exactly the amount of external work it does.
Heat content or Enthalpy 
- In isobaric process,
Qp = ∆U – W = (Uf – Ui) + p (Vf – Vi)
Qp = (Uf + p Vf) – (Ui + p Vi)
But H = U + pV ; where H = enthalpy = state function depending only on the state of the system and not on the path taken. Thus,
Qp = Hf – Hi = ∆H
- Thus, heat gained or lost in any isobaric process = change in enthalpy of the system.
- In endothermic reaction, heat is gained by system, so Qp > 0 and enthalpy increases.
- In exothermic reaction, heat is lost by system, so Qp < 0 and enthalpy decreases.
Molar specific heats of an ideal gas 
• Gas can be heated to a temp. T isometrically or isobarically.
• In isometric process, dUv = n cv dT.
• In isobaric process, dUp = n cp dT – p dV.
• From ideal gas equation, p V = n R T p dV = n R dT.
• Thus, for isobaric process, dUp = n cp dT – n R dT.
• Internal E. depends only on T change in internal E. is the same in both process.
• Thus, dUv = dUp n cv dT = n cp dT – n R dT cp – cv = R.
• For ideal gas, U = (3/2) n R T. Thus,
cv = (1 / n) ( dU / dT) = (1 / n) d / dT[(3 / 2) ( n R T)] = (3 / 2) R And cp = cv + R = (5 / 2) R.
• γ = cp / cv. (constant). cv, cp and γ vary according to type of gas:
cv = (3 / 2) R
cp = (5 / 2) R
γ = 5 / 3 = 1.67
cv = (5 / 2) R
cp = (7 / 2) R
γ = 7 / 5 = 1.40
cv = (7 / 2) R
cp = (9 / 2) R
γ = 9 / 7 = 1.29
Adiabatic processes for an ideal gas 
Adiabatic ---> Q = 0 ; W = p dV ---> dU = n cv dT = - p dV ---> dT = - p dV / n cv.
Since p V = n R T ---> p dV + V dp = n R dT = – (R / cv) p dV. Since R = cp – cv,
p dV + V dp = - [(cp – cv) / cv] p dV = (1 – γ) p dV. Dividing by (p V),
dV / V + dp / p = (1 – γ) dV / V ---> (dp / p) + (γ dV / V) = 0. Integrating the eqn,
ln p + γ ln V = constant ----> p (V) ^ γ = constant. Thus,
pi (Vi) ^ γ = pf (Vf) ^ γ
But p = n R T / V. Thus,
Ti (Vi) ^ (γ – 1) = Tf (Vf) ^ (γ – 1)
For isothermal process, p V = constant ----> p dV + V dp = 0.
Slopeisothermal = dp / dV ---> Slopeisothermal = – p / V.
For adiabatic process, p V ^ γ = constant ---> γ p (V) ^ (γ – 1) + (V ^ γ) dp = 0
Slopeadiabatic = dp / dV ---> Slopeadiabatic = – γ (p / V). Thus,
Slopeisothermal / Slopeadiabatic = γ
Wadiabatic = (pi Vi – pf Vf) / γ – 1
External Links 
UC Davis Thermal Energy Wiki - http://chemwiki.ucdavis.edu/Physical_Chemistry/Thermodynamics/State_Functions/THERMAL_ENERGY
Energy/Watt Calculator - http://www.mhi-inc.com/Converter/watt_calculator.htm