CHEMICAL ENGINEERING THERMODYNAMICS

Course no: CHE F 213 / C311

Dr. Srinivas Krishnaswamy

1st Semester 2012 2013

CHEMICAL ENGG. GROUP

BITS PILANI K. K. BIRLA GOA CAMPUS

Introduction to and basis for Second law Heat reservoir Heat engine Refrigerator and heat pump Direction of spontaneity of processes Impossibility of thermodynamic cycles Impossibility of a cycle involving only heat transfer Illustration of heat engines and refrigerators / heat pumps Kelvin Planck statement Clausius statement

We know that energy is a conserved property and no process violates the first law of thermodynamics It is reasonable to assume that a process must satisfy the 1st law to occur The 1st law however places no restriction on the direction in which a process will occur But satisfying the 1st law does not mean that the process will actually occur

A hot cup of coffee cools by virtue of heat transfer to the surrounding but the heat from the colder surrounding cannot flow in the cup and make the coffee hot again automatically A vehicle moving on road consumes heat energy as fuel which cannot be restored Transferring heat to a wire will not generate electricity Transferring heat to a paddle wheel will no cause it to rotate

Based on these observations of nature, we see that processes take place in a certain direction and not in the reverse direction While the first law gives a quantitative estimate it gives no information on whether a process will occur or not Answer to this is provided by the second law The reverse processes if at all they occur spontaneously end up violating the 2nd law

Violation of the 2nd law is detected using a property called entropy For a process / cycle to occur it must satisfy the 1st and 2nd law of thermodynamics While the first law discusses quantity the second looks at quality and degree of degradation of energy during a process The 2nd law is also used to determine the theoretical limits for performance of various engineering systems as well as predicting the degree of completion of various chemical reactions

It is a body with large heat capacity to and from which heat can be transferred without any change in temperature Some typical examples in nature are oceans, lakes, rivers, the atmosphere etc. A two phase system can be modelled as a heat reservoir since it can absorb and release large quantities of heat at constant temperature

A reservoir that supplies energy in the form of heat is called a source and one that absorbs energy in the form on heat is referred to as a sink This is a closed system with no work interaction A heat reservoir is always characterised by its temperature

This a thermodynamic system operating on a cycle to which net positive amount of heat is added and net positive amount of work is obtained Note the stress on the word net and operating on a cycle The latter implies that by operating just in a single process, it is not possible to obtain work continuously

 They

receive heat from a high temperature source They convert part of this heat into work They reject the remaining waste to a low temperature sink They operate on a cycle

It can thus be concluded that a device which would lead to complete conversion of heat into work is not possible Work cannot be obtained directly by simply adding heat to a system To convert heat to work, some special devices are required (earlier discussed heat engines)

In a similar manner a thermodynamic cycle involving heat transfer alone cannot be devised There must be a process in which some work must be done

The term heat engines in the broader sense include work producing devices that do not operate on a thermodynamic cycle, e.g. internal combustion engines, gas turbines etc. These operate on a mechanical cycle The working fluid does not undergo a complete cycle and is not returned to its original state

Note: cycle not complete thermodynamically

Note: cycle is complete thermodynamically

Note Qout is the magnitude of energy wasted in the environment in order to complete the cycle, but it can never be equal to zero Only a part of the heat input transferred is converted to work The fraction of heat input that is converted to work is a measure of performance of the heat engine

Performance in general can be expressed in terms of desired output and required input For heat engines the desired output is the net work output and the required input is the amount of heat supplied th = objective quantity / quantity that costs = net work output / total heat input

th = Wnet out / Qin

th = 1 (Qout / Qin)
Most devices operate between a high temperature and low temperature reservoir (between temperatures TH and TL th = 1 (QL / QH) < 1

Thermal efficiency is a measure of how efficiently an engine converts heat into work Increased efficiency means less fuel consumption, less costs and less pollution For large steam power plants th ~ 40% and that for diesel and petrol engines ~ 35% Thus even with the most efficient heat engines available today, almost half the energy supplied ends up in the heat sink

Since the condenser in the power plant rejects heat to the sink, can the condenser not be removed to increase efficiency? Unfortunately No For the simple reason that without this process, the cycle cannot be completed Only if the cycle is completed can continuous operation be obtained

Even under ideal conditions, the amount of heat supplied to the gas is greater than work done since part of the heat supplied goes to increase the temperature of gas (Part (a) of figure). Note from figure (Part (b)) that it is not possible to transfer 85 kJ of excess heat at 90 oC back to reservoir at 100 oC for further use Instead a low temperature reservoir is required, say at 20 oC so that gas can be returned to original state by rejecting excess energy as heat to this reservoir. This energy is waste heat and cannot be recycled

1.

2.

Heat is transferred to a heat engine from a furnace at a rate of 80 MW. If the rate of waste heat rejection to a nearby river is 50 MW, determine the net power output and the thermal efficiency of the heat engine A car engine with a power output of 50 kW has a thermal efficiency of 24%. Determine the fuel consumption rate of this car if the fuel has a heating value of 45000 kJ/kg (energy released per kg of fuel burned)

IT IS IMPOSSIBLE TO CONSTRUCT A DEVICE THAT WILL OPERATE IN A CYCLE AND PRODUCE NO OTHER EFFECT THAN THE RAISING OF A WEIGHT (PRODUCTION OF WORK) AND THE EXCHANGE OF HEAT WITH A SINGLE RESERVOIR

Refers to a heat engine

TH
QH

IMPOSSIBLE
W

The stress on operating on a cycle is significant The above statement like the first law is also valid for a thermodynamic cycle For a non-cyclic process it maybe possible to add heat to a system and get an equivalent amount of work out In an isothermal expansion of ideal gas for example, the change in internal energy is zero and the heat transfer is equal to the work done

Not really since the illustration represents a non-cyclic process However this cannot happen continuously An infinite source of high pressure gas is required An infinitely long cylinder is required The gas cannot expand indefinitely, whatever is the pressure to start with. The expansion will stop when the system reaches a pressure equal to that of the surroundings

IT IS IMPOSSIBLE TO CONSTRUCT A DEVICE THAT WILL OPERATE IN A CYCLE AND PRODUCE NO OTHER EFFECT THAN TRANSFER OF HEAT FROM A LOW TEMPERATURE BODY TO A HIGH TEMPERATURE BODY

Refers to a refrigerator / heat pump

QH

IMPOSSIBLE
QL
TL

The stress on the words operating on a cycle is significant here In a single process it may be possible to remove heat from a low temperature body without doing work For example, evaporation of refrigerant after initial throttling

We have two classical statements for the second law Both are equivalent and mean the same thing Violation of one implies violation of the other Truth of one implies the truth of the other

machine that violates the second law of thermodynamics Too good to be true Countless PMM2 proposed, but have turned up worthless Proposers of PMM2 generally have innovative minds, but lack formal engineering sense

Note: This violates first law, Energy is only created without any source

Can steam from the turbine be used to run pump, i.e. heat to work? Note: This violates second law

Second Law states that no heat engine can have an efficiency of 100 % The efficiency is always less than unity But the question is by how much? In other words what is the maximum efficiency possible? To understand this, one needs to understand the concept of reversibility and irreversibility

A reversible process is one that can be reversed without leaving any trace on the surroundings Processes that are not reversible are irreversible Are reversible processes ideal? For the moment it is safe to assume that they are. Then why bother about something that does not exist?

Reversible processes are easier to analyze and serve as idealized models to which actual processes can be compared and can be viewed as theoretical limits for the corresponding irreversible ones Performance of different devices designed to do same task can be compared on the basis of their efficiencies which a degree of approximation to corresponding reversible processes The better the design, lower the irreversibility and higher the efficiency

 Friction

Unrestrained

expansion Mixing of substances Combustion Flow of electricity through a resistor Heat transfer over a finite temperature difference

Essentially irreversible when a finite temperature difference exists No heat transfer possible without a finite temperature difference Surroundings will always gain heat during the process (for HT from low to high) Reversible heat transfer when the temperature difference for heat transfer is infinitesimal

process is internally reversible if no irreversibilities occur within the boundaries of the system, e.g. quasi-equilibrium systems, vapour-liquid eqm. A process is externally reversible if no irreversibilities occur outside the boundaries of the system

Departure from equilibrium is infinite, i.e. performed very slowly in a quasi-equilibrium manner No dissipative effects are present Process can be carried out in both directions and can be reversed at any intermediate stage Heat and work interactions between system and surroundings is the same in both directions

These are non-equilibrium processes Performed at a finite rate with a finite potential difference Dissipative effects exist Process occurs in only one direction The surroundings always loses work (lost work) and gains heat (waste heat) for all practical purposes

Understanding the importance of 2nd Law 2nd law statements and their equivalence Heat Engines and efficiency Concept of reversible processes