First and Second Laws of Thermodynamics

RAT 11b

Class Objectives
Understand and apply:
work, energy, reversibility, heat capacity First and Second Laws of Thermodynamics

Reversibility
Reversibility is the ability to run a process backwards and forwards infinitely without losses.

Money analogy
Reversible (no service fee) Dollars Pounds 100.00 40.00 100.00 40.00 100.00 40.00 100.00 40.00 100.00 40.00 Irreversible (5% service fee) Dollars Pounds 100.00 38.00 90.25 34.30 81.45 30.95 73.51 27.93 66.34 25.20

Day Monday Tuesday Wednesday Thursday Friday

Each morning, dollars are converted to pounds. Each evening, pounds are converted to dollars.

Pair Exercise 1 Using Excel, reproduce the previous table, except use a service charge of 10%.

Reversibility and Energy

Voltage
Pressure

Generator

Motor Pump Turbine

Electric Current

Fluid Flow

If irreversibilities were eliminated, these systems would run forever.

Perpetual motion machines
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Example: Popping a Balloon

A reversible process can go in either direction, but these processes are rare. Generally, the irreversibility shows up as waste heat

Not reversible without expending Not reversible unless energy energy is expended

Sources of Irreversibilities
Friction Voltage drops Pressure drops Temperature drops Concentration drops

Basic Laws of Thermodynamics

First Law of Thermodynamics
energy can neither be created nor destroyed

Second Law of Thermodynamics

naturally occurring processes are directional
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First Law of Thermodynamics

One form of work may be converted into another, or, work may be converted to heat, or, heat may be converted to work, but, final energy = initial energy

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2nd Law of Thermodynamics

We intuitively know that heat flows from higher to lower temperatures and NOT the other direction.
i.e., heat flows downhill just like water You cannot raise the temperature in this room by adding ice cubes.

Thus processes that employ heat are inherently irreversible.

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Heat/Work Conversions
Heat transfer is inherently irreversible. This places limits on the amount of work that can be produced from heat. Heat can be converted to work using heat engines
Jet engines (planes), steam engines (trains), internal combustion engines (automobiles)
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Heat into Work

W
High-temperature Source, Thot

(e.g., flame)

Qhot

Heat Engine

Qcold (e.g., cooling pond)

Low-temperature Sink, Tcold

A heat engine takes in an amount of heat, Qhot, and produces work, W, and waste heat Qcold. Nicolas Carnot (kar n) derived the limits of converting heat into work.

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Carnot Equation: Efficiency

Given the heat engine on the previous slide, the maximum work that can be produced is governed by:

where the temperatures are absolute temperatures. Thus, as Thot Tcold, Wmax 0. This ratio is also called the efficiency, h.
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Wmax Tcold 1 Qhot Thot

Pairs Exercise 2
Use Excel to create a graph showing the amount of work per unit heat for a heat engine in which the source temperature increases from 300 K to 3000 K and the waste heat is rejected to an ambient temperature of 300 K.

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Work into Heat

Although there are limits on the amount of heat converted to work, work may be converted to heat with 100% efficiency. This is shown by Joules experiment

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Joules Experiment
Joules Mechanical Equivalent of Heat
DT =

1o C

This proved 1 kcal = 4,184 J m Dx F E = FDx = 4,184 J

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1 kg H2O

Where did the energy go?

By the First Law of Thermodynamics, the energy we put into the water (either work or heat) cannot be destroyed. The heat or work added increased the internal energy of the water.

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Internal Energy
Translation Rotation Vibration Molecular Interactions
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Heat Capacity
An increase in internal energy increases the temperature of the medium. Different media require different amounts of energy to produce a given temperature change.

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Heat Capacity Defined

Heat capacity: the ratio of heat, Q, needed to change the temperature of a mass, m, by an amount DT:

Q C mDT

Sometimes called specific heat

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Heat Capacity for Constant Volume Processes (Cv)

insulation

DT Heat, Q added

Heat is added to a substance of mass m in a fixed volume enclosure, which causes a change in internal energy, U. Thus, Q = U2 - U1 = DU = m Cv DT
The v subscript implies constant volume
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Heat Capacity for Constant Pressure Processes (Cp)

Dx
DT m Heat, Q added m

Heat is added to a substance of mass m held at a fixed pressure, which causes a change in internal energy, U, AND some PV work.
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Cp Defined
Thus, Q = DU + PDV = DH = m Cp DT
The p subscript implies constant pressure
Note: H, enthalpy. is defined as U + PV, so dH = d(U+PV) = dU + VdP + PdV At constant pressure, dP = 0, so dH= dU + PdV For large changes at constant pressure DH = DU + PDV

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Experimental Heat Capacity

Experimentally, it is easier to add heat at constant pressure than constant volume, thus you will typically see tables reporting Cp for various materials (Table 21.2 in Foundations of Engineering).

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Pair Exercise 3
1. Calculate the change in enthalpy per lbm of nitrogen gas as its temperature decreases from 500 oF to 200 oF. 2. Two kg of water (Cv=4.2 kJ/kg K) are heated using 200 Btu of energy. What is the change in temperature in K? In oF?
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