First Law of Thermodynamics

The first law of thermodynamics is the application of the conservation of energy principle to heat and thermodynamic processes:

Index Heat engine concepts The first law makes use of the key concepts of internal energy, heat, and system work. It is used extensively in the discussion of heat engines. It is typical for chemistry texts to write the first law as U=Q+W. It is the same law, of course - the thermodynamic expression of the conservation of energy principle. It is just that W is defined as the work done on the system instead of work done by the system. In the context of physics, the common scenario is one of adding heat to a volume of gas and using the expansion of that gas to do work, as in the pushing down of a piston in an internal combustion engine. In the context of chemical reactions and process, it may be more common to deal with situations where work is done on the system rather than by it.

Enthalpy
Four quantities called "thermodynamic potentials" are useful in the chemical thermodynamics of reactions and non-cyclic processes. They are internal energy, the enthalpy, the Helmholtz free energy and the Gibbs free energy. Enthalpy is defined by

H = U + PV
where P and V are the pressure and volume, and U is internal energy. Enthalpy is then a precisely measurable state variable, since it is defined in terms of three other precisely definable state variables. It is somewhat parallel to the first law of thermodynamics for a constant pressure system

Q = U + PV since in this case Q=H

It is a useful quantity for tracking chemical reactions. If as a result of an exothermic reaction some energy is released to a system, it has to show up in some measurable form in terms of the state variables. An increase in the enthalpy H = U + PV might be associated with an increase in internal energy which could be measured by calorimetry, or with work done by the system, or a combination of the two. The internal energy U might be thought of as the energy required to create a system in the absence of changes in temperature or volume. But if the process changes the volume, as in a chemical reaction which produces a gaseous product, then work must be done to produce the change in volume. For a constant pressure process the work you must do to produce a volume change V is PV. Then the term PV can be interpreted as the work you must do to "create room" for the system if you presume it started at zero volume. Table of enthalpy changes

Index Internal energy concepts

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System Work
When work is done by a thermodynamic system, it is usually a gas that is doing the work. The work done by a gas at constant pressure is:

Example Index For non-constant pressure, the work can be visualized as the area under the pressure-volume curve which represents the process taking place. The more general expression for work done is: Heat engine concepts

Work done by a system decreases the internal energy of the system, as indicated in the First Law of Thermodynamics. System work is a major focus in the discussion of heat engines. HyperPhysics***** Thermodynamics
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Thermodynamics is a branch of physics which deals with the energy and work of a system. Thermodynamics deals only with the large scale response of a system which we can observe and measure in experiments. In aerodynamics, we are most interested in thermodynamics in the study of propulsion systems and understanding high speed flows. The state of a gas is defined by several properties including the temperature, pressure, and volume which the gas occupies. From a study of the first law of thermodynamics, we find that the internal energy of a gas is also a state variable, that is, a variable which depends only on the state of the gas and not on any process that produced that state. We are free to define additional state variables which are combinations of existing state variables. The new variables often make the analysis of a system much simpler. For a gas, a useful additional state variable is the enthalpy which is defined to be the sum of the internal energy E plus the product of the

pressure p and volume V. Using the symbol H for the enthalpy: H=E+p*V The enthalpy can be made into an intensive, or specific , variable by dividing by the mass. Propulsion engineers use the specific enthalpy in engine analysis more than the enthalpy itself. How does one use this new variable called enthalpy? Let's consider the first law of thermodynamics for a gas. For a system with heat transfer Q and work W, the change in internal energy E from state 1 to state 2 is equal to the difference in the heat transfer into the system and the work done by the system: E2 - E1 = Q - W The work and heat transfer depend on the process used to change the state. For the special case of a constant pressure process, the work done by the gas is given as the constant pressure p times the change in volume V: W = p * [V2 - V1] Substituting into the first equation, we have: E2 - E1 = Q - p * [V2 - V1] Let's group the conditions at state 2 and the conditions at state 1 together: (E2 + p * V2) - (E1 + p * V1) = Q The (E + p * V) can be replaced by the enthalpy H. H2 - H1 = Q From our definition of the heat transfer, we can represent Q by some heat capacity coefficient Cp times the temperature T. (H2 - H1) = Cp * (T2 - T1)

At the bottom of the slide, we have divided by the mass of gas to produce the specific enthalpy equation version. (h2 - h1) = cp * (T2 - T1) The specific heat capacity cp is called the specific heat at constant pressure and is related to the universal gas constant of the equation of state. This final equation is used to determine values of specific enthalpy for a given temperature. Enthalpy is used in the energy equation for a fluid. Across shock waves, the total enthalpy of the gas remains a Thermodynamic potentials Internal energy U(S,V) Helmholtz free energy Enthalpy Gibbs free energy constant. Enthalpy In thermodynamics and molecular chemistry, the enthalpy or heat content (denoted as H or H, or rarely as ) is a quotient or description of thermodynamic potential of a system, which can be used to calculate the "useful" work obtainable from a closed thermodynamic system under constant pressure. The term enthalpy is composed of the prefix en-, meaning to "put into", plus the Greek word -thalpein, meaning "to heat", although the original definition is thought to have stemmed from the word, "enthalpos" It is often calculated as a differential sum, describing the changes within exo- and endothermic reactions, which minimize at equilibrium. A(T,V) = U TS H(S,p) = U + pV G(T,p) = U + pV TS edit

Contents [hide] 1 History o 1.1 Original Definition 2 Application and extended formula o 2.1 Overview o 2.2 Relationships o 2.3 Heats of reaction o 2.4 Open systems 3 Standard enthalpy changes o 3.1 Definitions 3.1.1 Examples: Inorganic compounds (at 25 C) 4 Specific enthalpy 5 Notes 6 References 7 See also

8 External links

[edit] History Over the history of thermodynamics, several symbols have been used to denote what is now known as the enthalpy of a system. Originally, it is thought that the word "enthalpy" was created by Benoit Paul mile Clapeyron and Rudolf Clausius through the publishing of the Clausius-Clapeyron relation in "The Mollier Steam Tables and Diagrams" in 1927, but it was later published that the earliest recording of the word was in 1875, by Josiah Willard Gibbs in the publication "Physical Chemistry: an Advanced Treatise"[2], although it is not referenced in Gibbs' works directly[3]. In 1909, Keith Landler discussed Gibbs' work on the 'heat function for constant pressure' and noted that Heike Kamerlingh Onnes had coined its modern name from the Greek word "enthalpos" () meaning "to put heat into." [1] [edit] Original Definition This is the heat change which occurs when 1 mol of a substance reacts completely with oxygen to form products at 298K and 1 atm. The function H was introduced by the Dutch physicist Heike Kamerlingh Onnes in early 20th century in the following form:

where E represents the energy of the system. In the absence of an external field, the enthalpy may be defined, as it is generally known, by:

but can also be surmised into one formula as;

where (all units given in SI)

H is the enthalpy (joules) U is the internal energy, (joules) p is the pressure of the system, (pascals) V is the volume, (cubic meters)

[edit] Application and extended formula [edit] Overview In terms of thermodynamics, enthalpy can be calculated by determining the requirements for creating a system from "nothingness"; the mechanical work required, PV differs, based upon the Constance of conditions present at the creation of the thermodynamic system. Internal energy, U, must be supplied to remove particles from a surrounding in order to allow space for the creation of a system, providing that environmental variables, such as pressure (p) remain constant. This internal energy also includes the energy required for activation and the breaking of bonded compounds into gaseous species. This process is calculated within enthalpy calculations as U + PV, to label the amount of energy or work required to "set aside space for" and "create" the system; describing the work done by both the reaction or formation of systems, and the surroundings. For systems at constant pressure, the change in enthalpy is the heat received by the system plus the non-mechanical work that has been done. Therefore, the change in enthalpy can be devised or represented without the need for compressive or expansive mechanics; for a simple system, with a constant number of particles, the difference in

enthalpy is the maximum amount of thermal energy derivable from a thermodynamic process in which the pressure is held constant. [edit] Relationships As an expansion of the first law of thermodynamics, enthalpy can be related to several other thermodynamic formulae. As with the original definition of the first law; Where, as defined by the law; dU represents the infinitesimal increase of the systematic or internal energy. Q represents the infinitesimal amount of energy attributed or added to the system. W represents the infinitesimal amount of energy acted out by the system on the surroundings. As a differentiating expression, the value of H can be defined as

Where

represents the inexact differential. Q = TdS is the energy added by heating during a reversible process, dS is the increase in entropy (joules per Kelvin), dV is an infinitesimal volume

U is the internal energy, W = pdV is the work done by the system in a reversible process. P is the constant pressure T is the temperature (Kelvin)

For a process that is not reversible, the second law of thermodynamics states that the increase in heat Q is less than or equal to the product TdS of temperature T and the increase in entropy dS; thus

It is seen that, if a thermodynamic process is isobaric (i.e., occurs at constant pressure), then dP is zero and thus

The difference in enthalpy is the maximum thermal energy attainable from the system in an isobaric process. This explains why it is sometimes called the heat content. That is, the integral of dH over any isobar in state space is the maximum thermal energy attainable from the system. If, in addition, the entropy is held constant as well, i.e., dS = 0, the above equation becomes:

with the equality holding at equilibrium. It is seen that the enthalpy for a general system will continuously decrease to its minimum value, which it maintains at equilibrium . In a more general form, the first law describes the internal energy with additional terms involving the chemical potential and the number of particles of various types. The differential statement for dH is then:

where i is the chemical potential for an i-type particle, and Ni is the number of such particles. It is seen that, not only must the Vdp term be set to zero by requiring the pressures of the initial and final states to be the same, but the idNi terms must be zero as well, by requiring that the particle numbers remain unchanged. Any further generalization will add even more terms whose extensive differential term must be set to zero in order for the interpretation of the enthalpy to hold. [edit] Heats of reaction The total enthalpy of a system cannot be measured directly; the enthalpy change of a system is measured instead. Enthalpy change is defined by the following equation:

where H is the enthalpy change Hfinal is the final enthalpy of the system, measured in joules. In a chemical reaction, Hfinal is the enthalpy of the products. Hinitial is the initial enthalpy of the system, measured in joules. In a chemical reaction, Hinitial is the enthalpy of the reactants. For an exothermic reaction at constant pressure, the system's change in enthalpy is equal to the energy released in the reaction, including the energy retained in the system and lost through expansion against its surroundings. In a similar manner, for an endothermic reaction, the system's change in enthalpy is equal to the energy absorbed in the reaction, including the energy lost by the system and gained from compression from its surroundings. A relatively easy way to determine whether or not a reaction is exothermic or endothermic is to determine the sign of H. If H is positive, the reaction is endothermic, that is heat is absorbed by the system due to the products of the reaction having a greater enthalpy than the reactants. The product of an endothermic reaction will be cold to the touch. On the other hand if H is negative, the reaction is exothermic, that is the overall decrease in enthalpy is achieved by the generation of heat. The product of an exothermic reaction will be warm to the touch. Although enthalpy is commonly used in engineering and science, it is impossible to measure directly, as enthalpy has no datum (reference point). Therefore enthalpy can only accurately be used in a closed system. However, few real world applications exist in closed isolation, and it is for this reason that two or more closed systems cannot be compared using enthalpy as a basis, although sometimes this is done erroneously. [edit] Open systems In thermodynamic open systems, matter may flow in and out of the system boundaries. The first law of thermodynamics for open systems states: the increase in the internal energy of a system is equal to the amount of energy added to the system by matter flowing in and by heating, minus the amount lost by matter flowing out and in the form of work done by the system. The first law for open systems is given by:

where Uin is the average internal energy entering the system and Uout is the average internal energy leaving the system

During steady, continuous operation, an energy balance applied to an open system equates shaft work performed by the system to heat added plus net enthalpy added. The region of space enclosed by open system boundaries is usually called a control volume, and it may or may not correspond to physical walls. If we choose the shape of the control volume such that all flow in or out occurs perpendicular to its surface, then the flow of matter into the system performs work as if it were a piston of fluid pushing mass into the system, and the system performs work on the flow of matter out as if it were driving a piston of fluid. There are then two types of work performed: flow work described above which is performed on the fluid (this is also often called PV work) and shaft work which may be performed on some mechanical device. These two types of work are expressed in the equation:

Substitution into the equation above for the control volume cv yields:

The definition of enthalpy, H, permits us to use this thermodynamic potential to account for both internal energy and PV work in fluids for open systems:

During steady-state operation of a device (see turbine, pump, and engine), the expression above may be set equal to zero. This yields a useful expression for the power generation or requirement for these devices in the absence of chemical reactions:

This expression is described by the diagram above. [edit] Standard enthalpy changes [edit] Definitions Standard enthalpy change of combustion Standard enthalpy of combustion is defined as the enthalpy change observed in a constituent thermodynamic system when 1 mole of a substance reacts completely with oxygen under standard conditions.

Standard enthalpy change of hydrogenation Standard enthalpy of hydrogenation is the enthalpy change observed in a constituent thermodynamic system, when one mole of an unsaturated compound reacts completely with an excess of hydrogen under standard conditions to form a saturated compound.

Standard enthalpy change of formation Standard enthalpy change of formation is defined as the enthalpy change observed in a constituent thermodynamic system when a compound is formed from its elementary antecedents under standard conditions.

The standard enthalpy change of reaction (denoted H or Ho) is the enthalpy change that occurs in a system when 1 equivalent of matter is transformed by a chemical reaction under standard conditions. A common standard enthalpy change is the standard enthalpy change of formation, which has been determined for a vast number

of substances. The enthalpy change of any reaction under any conditions can be computed, given the standard enthalpy change of formation of all of the reactants and products. Other reactions with standard enthalpy change values include combustion (standard enthalpy change of combustion) and neutralisation (standard enthalpy change of neutralisation). [edit] Examples: Inorganic compounds (at 25 C) Chemical Compound Ammonia Ammonia Sodium carbonate Sodium chloride (table salt) Sodium chloride (table salt) Sodium chloride (table salt) Sodium chloride (table salt) Sodium hydroxide Sodium hydroxide Phase (matter) aq g s Chemical formula NH3 NH3 Na2CO3 Hf0 in kJ/mol -80.8 -46.1 -1131

aq

NaCl

-407

NaCl

-411.12

NaCl

-385.92

NaCl

-181.42

aq s

NaOH NaOH

-469.6 -426.7

Sodium nitrate Sodium nitrate Sulfur dioxide Sulfuric acid Silica Nitrogen dioxide Nitrogen monoxide Water Water Carbon dioxide Hydrogen Fluorine Chlorine

aq s g l s g g l g g g g g

NaNO3 NaNO3 SO2 H2SO4 SiO2 NO2 NO H2O H2O CO2 H2 F2 Cl2

-446.2 -424.8 -297 -814 -911 +33 +90 -286 -241.8 -393.5 0 0 0

Bromine Bromine

l g

Br2 Br2

0 0

(State: g - gaseous; l - liquid; s - solid; aq = aqueous) [edit] Specific enthalpy The specific enthalpy of a working mass is a property of that mass used in thermodynamics, defined as where u is the specific internal energy, p is the pressure, and v is specific volume. In other words, h = H / m where m is the mass of the system. The SI unit for specific enthalpy is joules per kilogram.