There are two classical statements of the second law of thermodynamics:

Kelvin & Planck "No (heat) engine whose working fluid undergoes a cycle can absorb heat from a single reservoir, deliver an equivalent amount of work, and deliver no other effect" Clausius "No machine whose working fluid undergoes a cycle can absorb heat from one system, reject heat to another system and produce no other effect"
Both statements of the second law place constraints on the first law by identifying that energy goes downhill. The second law is concerned with entropy (S). Entropy is produced by all processes and associated with the entropy production is the loss of ability to do work. The second law says that the entropy of the universe increases. An increase in overall disorder is therefore spontaneous. If the volume and energy of a system are constant, then every change to the system increases the entropy. If volume or energy change, then the entropy of the system actually decrease. However, the entropy of the universe does not decrease. For energy to be available there must be a region with high energy level and a region with low energy level. Useful work must be derived from the energy that would flows from the high level to the low level.

100% of the energy can not be transformed to work Entropy can be produced but never destroyed

Efficiency of a heat machine

The efficiency of a heat machine working between two energy levels is defined in terms of absolute temperature: = ( Th - Tc ) / Th = 1 - Tc / Th(1) where = efficiency Th = temperature high level (K) Tc = temperature low level (K) As a consequence, to attain maximum efficiency the Tc would have to be as cold as possible. For 100% efficiency the Tc would have to equal 0 K. This is practically impossible, so the efficiency is always less than 1 (less than 100%).

Change in entropy > 0 irreversible process

Change in entropy = 0 reversible process

Change in entropy < 0 impossible process

Entropy is used to define the unavailable energy in a system. Entropy defines the relative ability of one system to act on an other. As things move toward a lower energy level, where one is less able to act upon the surroundings, the entropy is said to increase.

For the universe as a whole the entropy is increasing!

Entropy definition

Entropy is defined as : S = H / T (2) where S = entropy (kJ/kg K) H = enthalpy (kJ/kg) T = absolute temperature (K) A change in the entropy of a system is caused by a change in its heat content, where the change of entropy is equal to the heat change divided by the average absolute temperature (Ta): dS = dH / Ta (3) The sum of (H / T) values for each step in the Carnot cycle equals 0. This only happens because for every positive H there is a countering negative H, overall.

Carnot Heat Cycle In a heat engine, a gas is reversibly heated and then cooled. A model of the cycle is as follows: State 1 --(isothermal expansion) --> State 2 --(adiabatic expansion) --> State 3 --(isothermal compression) --> State 4 --(adiabatic compression) --> State 1 State 1 to State 2: Isothermal Expansion Isothermal expansion occurs at a high temperature Th, dT = 0 and dE1 = 0. Since dE = H + w, w1 = - H1. For ideal gases, dE is dependent on temperature only. State 2 to State 3: Adiabatic Expansion The gas is cooled from the high temperature, Th, to the low temperature, Tc. dE2 = w2 and H2 = 0(adiabatic). State 3 to State 4: Isothermal Compression This is the reverse of the process between states 1 and 2. The gas is compressed at Tc. dT = 0 anddE3 = 0. w3 = - H3 State 4 to State 1: Adiabatic Compression This is the reverse of the process between states 2 and 3. dE4 = w4 and H4 = 0 (adiabatic). The processes in the Carnot cycle can be graphed as the pressure vs. the volume. The area enclosed in the curve is then the work for the Carnot cycle because w = integral (P dV). Since this is a cycle, dE overall equals 0. Therefore, -w = H = H1 + H2 + H3 + H4 If you decrease Tc, then the quantity -w gets larger in magnitude. if -w > 0 then H > 0 and the system, the heat engine, does work on the surroundings.

The laws of thermodynamics were determined empirically (by experiment). They are generalizations of repeated scientific experiments. The second law is a generalization of experiments dealing with entropy--it is that the dS of the system plus the dS of the surroundings is equal to or greater then 0.

Entropy is not conserved like energy!

Example - Entropy Heating Water

A process raises 1 kg of water from 0 to 100 C (273 to 373 K) under atmospheric conditions. Specific enthalpy at 0 C (hf) = 0 kJ/kg (from steam tables) (Specific - per unit mass) Specific enthalpy of water at 100 C (hf) = 419 kJ/kg (from steam tables) Change in specific entropy: dS = dH / Ta = ((419 kJ/kg) - (0 kJ/kg)) / ((273 K) + (373 K)) / 2 = 1.297 kJ/kgK
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Example - Entropy Evaporation Water to Steam

A process changes 1 kg of water at 100 C (373 K) to saturated steam at 100 C (373 K) under atmospheric conditions. Specific enthalpy of steam at 100 C (373 K) before evaporating = 418 kJ/kg (from steam tables) Specific enthalpy of steam at 100 C (373 K) after evaporating = 2675 kJ/kg (from steam tables) Change in specific entropy: dS = dH / Ta = ((2675 kJ/kg) - (418 kJ/kg)) / ((373 K) + (373 K)) / 2 = 6.054 kJ/kgK The total change in specific entropy from water at 100 C to saturated steam at 100 C is the sum of the change in specific entropy for the water, plus the change of specific entropy for the steam.
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Example - Entropy Superheated Steam

A process superheats 1 kg of saturated steam at atmospheric pressure to 150 C (423 K). Specific total enthalpy of steam at 100 C (373 K) = 2675 kJ/kg (from steam tables) Specific total enthalpy of superheated steam at 150 C (423 K) = 2777 kJ/kg (from steam tables) Change in specific entropy: dS = dH / Ta = ((2777 kJ/kg) - (2675 kJ/kg)) / ((423 K) + (373 K)) / 2
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= 0.256 kJ/kgK

The Second Law of Thermodynamics

Many texts define the second law as the entropy of the universe increases during any spontaneous process and then throw qrev/T or free energy = G and S at you. Thats too complex too fast. Well see that the second law and entropy are simple, at the level of first-year university chem. The second law is based on human experience. It doesnt come from complicated theory and equations. So, think of these experiences that you have had: A rock will fall if you lift it up and then let go. Hot frying pans cool down when taken off the stove. Iron rusts (oxidizes) in the air. Air in a high-pressure tire shoots out from even a small hole in its side to the lower pressure atmosphere. Ice cubes melt in a warm room. Whats happening in each of those processes? Energy of some kind is changing from being localized ("concentrated" in the rock or the pan, etc.) to becoming more spread out. Look at those examples again to see how that statement fits them all. OK? Thats it a simple way of stating fundamental science behind the second law: Energy spontaneously disperses from being localized to becoming spread out if it is not hindered from doing so. But what about entropy and universe that is in so many textbooks and may be in yours? Well see what entropy is in a minute. But the universe just means the system youre looking at PLUS its surroundings, i.e., everything thats close around it. System plus surroundings. If that system plus surroundings bothers you, or if you want details of three of the processes mentioned above, read the next paragraphs. If not, skip down to What Is Entropy, REALLY?

1. The rock has potential energy localized in it when you lift it up above the ground. Drop it and that PE changes to kinetic energy (energy of movement), pushing air aside as it falls (therefore spreading out the rocks KE a bit) before it hits the ground, dispersing a tiny bit of sound energy (compressed air) and causing a little heating of the ground it hits and the rock itself. The rock is unchanged (after a minute when it disperses to the air the small amount of heat it got from hitting the ground). But the potential energy that your muscles localized in by lifting it up is now totally spread out and dispersed all over in a little air movement and a little heating of the air and ground. [System: rock above ground, then on ground. Surroundings: air plus ground.] 2. The iron atoms in a hot frying pan are vibrating very rapidly (like dancing in place fast) and therefore the motional energy in the hot pan is localized. That motional energy will spread out if it can. Whenever the less rapidly moving molecules in the cooler air of the room hit the hot pan, the fast-vibrating iron atoms transfer some of their energy to the air molecules. The pans localized energy thus becomes dispersed, spread out more widely to molecules in the room air. [System: pan. Surroundings: room air.] 3. Iron in nails or other objects doesnt have to be hot (i.e., with very fast moving atoms or molecules) to have localized energy within it in a chemical sense: Iron atoms plus oxygen molecules of the air have more energy localized within their BONDS than does iron rust (iron oxide). (Thats why iron reacts with oxygen to release energy from their higher energy bonds and form the lower energy bonds in iron oxide, with all that difference in energy being dispersed to the surroundings as heat i.e., the reaction is exothermic and makes molecules in the surroundings move faster . But don't forget that even substances with lots of energy in their bonds are hindered extremely! from immediately spreading out that energy. It takes much energy to break the bonds just before or as they react, even though far more energy may be then given out as the result of the reaction as the new bonds form.) Therefore, even in moist air that speeds up the process, iron spontaneously (but not very rapidly) reacts with oxygen

and each spreads out some of its bond energy to the surroundings when the iron and oxygen form iron oxide. [System: iron and oxygen, iron oxide. Surroundings: the nearby air and any moisture or salt in the air plus any object in contact with the rusting iron.]
What Is Entropy, REALLY?

Entropy measures the spontaneous dispersal of energy: how much energy is spread out in a process, or how widely spread out it becomes at a specific temperature. (Sometimes, its a simple equation, Entropy change = energy dispersed/T, or qreversible/T , as in phase changes like melting or vaporization where S = Hfusion /T or Hvaporization /T, respectively.)
(In chemistry the energy that entropy measures as dispersing is motional energy, the translational and vibrational and rotational energy of molecules [Figure 1 of http://2ndlaw.oxy.edu/entropy.html ] and the H of phase change energy both motional or phase change energy being designated either as "q" or H in many equations. Bond energy, the potential energy associated with chemical bonds that we talked about in the iron oxidation example, is only measured by entropy change in connection with a chemical reaction in G = H - T S

Is that description of an entropy change complicated? Entropy is a sophisticated kind of "before and after" yardstick measuring how MUCH energy is spread out/T as a result of a process, or how WIDELY spread out is the energy after something happens than before (at a constant temperature). Maybe entropy seems confusing and abstract when the first entropy equation is thrown at you in your text, about a change in entropy in a reversible process: S = qrev / T. Lets look at it by using a how MUCH practical example: ice spontaneously melting in a warm room. (Phase change S, an increase in entropy)
Phase Change a how much energy is dispersed example

From your experience remember, thats the basis of the second law what direction do you think the energy of molecules would go from those faster moving air molecules in the warm

room to the slower moving water molecules in the cold ice ... or would the slower moving molecules in the ice give up some of their energy to the warm air? Sure. From the hotter to the colder! Always. [If you need a math proof, it is given in the middle of http://secondlaw.oxy.edu/six.html] The greater motional energy of the warmer air molecules spreads out some energy to the cold ice and this breaks (or alters) intermolecular hydrogen bonds between the water molecules in the ice. Liquid water forms at the tiniest temperature above the melting point of 0oC (273 K) and, reversibly, solid ice forms at the tiniest temperature below 0oC.
As the warmer air molecules transfer some of their motional energy to be dispersed in the ice, it breaks many hydrogen bonds in the ice. This allows the molecules to move with the same amount of energy that they had when just "dancing in place" in the ice but now form new bonds with other water molecules, and actually move a little bit, but thats a lot compared to being in one place in a solid. ( Their speed is not increased, and thus the resulting liquid's total motional energy is unchanged, and the temperature doesn't rise above 273 K when ice melts to water.) Even though there is an increase only in the potential energy of the liquid water at 273 K compared to ice, no longer are all the molecules held in the very rigid framework of ice. They still are hydrogen bonded in the liquid but constantly move through space by forming new bonds after breaking others.

How MUCH energy is dispersed in melting ice, breaking those original H-bonds and allowing the molecules to move relatively freely? The enthalpy of fusion, Hfusion , of course! Thats why your text says the entropy increase in melting is S = qrev /T = H/T.
Standard Entropy a how much energy is dispersed example

Then, many texts go on to talk about standard entropies, S 298 , of all kinds of elements and compounds. Actually, standard entropies should be called standard entropy changes for substances. This is because the entropy values of So298 that are listed in Tables come from the total amount of energy (qrev ) that has had to be reversibly spread out (at each incremental fraction of temperature, i.e., qrev/T) in any substance as it was very slowly heated up from 0 K to 298 K a big change from 0 entropy at 0 K to So at 298 K.
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Texts usually urge you to look at So298 values to see the differences between the standard entropies of different types of molecules monatomic gases vs. polyatomic, gases vs liquids of the same element, graphite vs. diamond vs. metals vs iodine. However, some texts fail to tell you that these S o298 numbers show a rough comparative amount of motional energy (plus any phase change energy given to the substance from 0 K) that each particular substance must have to exist at 298 K substances that are capable of more free motion need to have more energy spread out in them or they just could not be at 298 K. Specifically, monatomic gases dont require any energy to rotate, but polyatomic gases do and the more different kinds of turning and wiggling in large molecules, the greater the energy required and the larger is the S o value. Graphite has a relatively loose structure, a less rigidly bonded solid than diamond; therefore, graphite requires more energy for the normal slight movement in its crystals than does diamond with its lesser possible movement. Iodine molecules are much less strongly bound by intermolecular attractions to other I 2 molecules that are metal atoms kept in place in their sea of electrons; thus iodine has a higher So value because it requires more energy for its molecules to vibrate a bit at 298 K than do held in place iron or copper or gold atoms.

Volume Increase: Gas expansion, gases mixing, liquids mixing how widely examples

Most texts show before and after illustrations of a gas spontaneously expanding into an evacuated bulb. When that happens, theres no energy change, no temperature change. Thus, the total motional energy of the initial gas in one bulb is spread out to be half that amount of energy (and half the molecules of gas) in in each of the two bulbs finally. WHY should a gas behave this way? Your text may use that kind of illustration and then talk about calculating the probability of the gas all being in one bulb versus being in two with little red dots for energetically colliding molecules and tables for calculations. (But those texts dont emphasize the energy of those little molecules that are racing around and hitting each other!) If your text does that kind of calculation, go along with it; memorize it; youre going to have it on an exam. But "probabilities" are just half the reason for the gas expanding; they are the math for the results (that would not have occurred if motionally energetic molecules hadnt been part of the system. Marbles or dice or playing cards dont move to other places no matter what their probability arrangement might be!!). YOU know the simplified explanation for a gas to move into an evacuated bulbthe second law of thermodynamics as does any energy, the motional energy of the molecules (translation and

rotation) spreads out as widely as it can, if it is not hindered. (It certainly wasnt hindered from spreading out just as soon as that stopcock between the two bulbs was opened!) More fundamentally, if there are particles with motional energy AND there is an increased space that probability shows could be occupied, those particles will spread out widely and the entropy of the gas will increase. Wider energy dispersal = entropy increase. How to calculate the entropy increase in the spontaneous expansion process is not obvious, because (1) there isn't any change in the energy of the gas that expands (q = 0), (2) even if there was a change in energy, you couldn 't use the simple equation with qrev/T because it is an irreversible process unlike the reversible melting of ice at 273 K! It isnt a how much energy is dispersed situation, its a question of how more widely spread out in two bulbs is the gas than it was in one. (Of course, from the definition of entropy as a spontaneous increase in energy dispersal, there is an entropy increase in the expansion because the energy of the gas has obviously spread out more.) In your text probably this entropy increase is calculated from the energy required to reversibly compress the gas back to the volume of one bulb, i.e., RT ln (V2/V1) and thus S = R ln (V2/V1)
Gases spontaneously mix a how widely energy is dispersed example;

If you put two different gases in that same two-bulb apparatus we talked about just now but both at the same atmospheric pressure when you opened the stopcock, they would slowly spontaneously mix. Why? Just the second law, of course! The molecules of each gas are rapidly moving and colliding; they have motional energy. So, as the second law predicts, the motional energy in those molecules will cause them to spread out if it is not hindered. Sure enough, when you open the stopcock, you are letting the motional energy of each gas spread out more widely into the larger volume of two bulbs rather than staying in one. Is the probability that there are more positions in two bulbs for the molecules than there are in one important? Yes. Even though our simple predictions based on energy dispersal always works, technically and fundamentally, entropy change requires both the

presence of molecules that have motional energy and also calculations that show that it is more probable for such particles to be in two rather than one volume.
Liquids spontaneously mix (if they are like each other) a how widely example

When liquid water and alcohol are added to one another, they spontaneously mix as do any like (similar to each other in chemical structure) liquids. This is true regardless of volume change because the mere presence of two substances in the same total volume involves a dispersal of the energy of each in that whole mixture and increased dispersal and greater entropy change as the relative quantities of each liquid in the mixture increases toward a 50:50 mole ratio. This is one of several cases in which the simple view of energy becoming more dispersed when substances are mixed works i.e., predicts the correct result of spontaneity and of entropy increase. However, the fundamental calculations are relatively complex and involve statistical mechanics in which the solution is considered to be in many cells with each cell a different combination of molecules in the ratio of the quantities of the two liquids present. The equation for the entropy increase in the mixture uses the relative molar quantities of liquids that were mixed.
A small amount of solute is added to a solvent a how widely example

When even a small amount of solid solute is added to a solvent, just as in the mixtures of liquids above, the motional energy of the individual solvent molecules (and the solute molecules) in the new solution is each more separated from its own type of molecule than before, and thus each individual molecules energy is more spread out or dispersed. The entropy of the solvent and the solute each increases in the solution. (The more fundamental reasoning and resulting equations from statistical mechanics are the same as described above for liquid mixtures.) If we realize that a solvents energy is more dispersed in a solution than when it is a pure solvent, we can see why a solvent in a solution should be increased in entropy compared to its entropy as a pure solvent. Then also, it is obvous that the entropy will be larger depending on how many molecules of solute are added to the solvent. That increased entropy of the solvent in a solution is the cause of the "colligative

effects" that we study: (1) osmotic pressure, (2) boiling point elevation, and (3) freezing point depression. Now, if the solvent tends to stay in a solution (because its energy is more dispersed there), rather than being with only with its own kind of molecules in pure solvent, it will stay in that solution if it has a choice! That means (1) if there is a membrane placed between a pure solvent and a solution containing it (and that membrane allows solvent molecules from pure solvent to go through it from the other side but not the solute molecules), pure solvent will go through the membrane to get to the solution because its energy is more spread out there. Thats osmosis, a very important phenomenon in biochemistry; (2) solvent molecules in a solution will not leave that solution to become vapor molecules in the atmosphere above a solution as readily as at the normal boiling point of the pure solvent; a higher temperature will be necessary to cause enough molecules to leave the solution to be in equilibrium with the atmospheric pressure and boil; (3) solvent molecules in a solution will not be in equilibrium with the solid phase (composed of pure solvent molecules) at the normal freezing point; a lower temperature is necessary to reduce the motional energy of the solvent molecules so that they can make intermolecular bonds to form a solid; i.e., be in equilibrium with their molecules in the solid phase), All of these colligative effects increase as the amount of solute in the solvent is increased because the entropy (i.e., energy dispersal) of the solvent increases in the solution with a greater concentration of solute.
Heating a substance a how much energy is dispersed example

Textbooks that do not use calculus omit this example, but it can easily be described qualitatively because we know the basic idea energy spontaneously spreads out if it is not hindered. Motional energy from hot surroundings is spontaneously spread out in cooler systems/substances, never the other way around. The entropy of the cooler system always increases more as it is heated than the hot surroundings decrease in entropy. (Calculations are available at http://entropysite.oxy.edu/entropy_isnot_disorder.html#m3 )
Chemical reactions how much and "how widely energy is dispersed

Spontaneous exothermic reactions are usually due to the chemical bonds in the reactants being relatively weaker than the bonds in the products. (What you actually calculate in the H change of a reaction is the enthalpy ["heat"] of formation of products minus the enthalpy of formation of reactants. Enthalpies of formation are closely related to bond strengths/energies) That how much energy difference of H in a chemical reaction is spread out as old bonds are being broken and new ones formed by the product molecules (and any unreacted molecules of reactant) in moving much more rapidly than the reactant molecules did at the original T. Then, this motional energy of the products is dispersed to the surroundings and the temperature of the system returns to T. Now, consider the entropy change in a reaction. It is the reactants motional energy (plus any phase change energy in them) that determines the value/magnitude of the entropy state of each reactant at T. Then, because the entropy values of possible products at T are usually different than those of the reactants, the S in the reaction is easily calculated from Sproducts Sreactants . That difference is a combination of how much and how widely is energy dispersed in the reaction process whether heat is evolved or absorbed and whether the volume changes or more mixtures are formed. (Thus, the S change alone can be responsible for a spontaneous reaction even though most often it either simply adds to or subtracts from the usually larger H change.)
Both kinds of energy difference (i.e., how much and how widely) are combined in the S change you calculate, but often you can estimate whether the S change in a reaction is greater or lesser simply by estimating the how widely factor of energy spreading out in the products as compared to the reactants. This is the scientific reason for the textbook rules of entropy increase in reactions: (1) if more molecules are produced, this involves how widely (motional energy is more widely spread out if there are more molecules among which it is dispersed); (2) if a phase change from a solid to a liquid occurs (a phase change involves how much, an increase in potential energy from that in solids to liquids, and how widely, less restricted locations in space in a liquid allow energy to be more spread out); (3) if a gas is produced from a solid or liquid (as stated in (2), the process involves a phase change in which both how much and how widely energy is more dispersed.)

Spontaneous endothermic reactions are due to the greater motional energy in the hotter surroundings that can be transferred

to reactants in a system. As you know from the Gibbs equation, G = H TS, a high temperature makes the TS function dominate. Thus, entropy change is causal in endothermic reactions. In the Gibbs equation, G = H TS, each term describes an aspect of the energy that is dispersed because of a chemical reaction occurring in a system: G is the total energy that is spread out in the universe (system plus surroundings) due to the reaction that has taken place in the system. H is the energy from the reaction that is dispersed from the system to the surroundings. TS is the energy that is dispersed in the system in the products of the reaction as compared to the reactants. If each term is divided by T, the Gibbs can be seen as an all entropy equation. The Gibbs works because it corresponds to the second law as we would state it, Energy spontaneously disperses, if it is not hindered. When it does so, entropy increases in the combination of system plus surroundings. This is what the conventional statement means when it says more succinctly but more obscurely, The entropy of the universe increases during any spontaneous process.