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Chem 340 - Lecture Notes 3 - Fall 2013 - Heat and Work and Energy
Chem 340 - Lecture Notes 3 - Fall 2013 - Heat and Work and Energy
Thermodynamics at its core is about energy, the flow of energy from one substance or
system to another i.e. use of energy to do work, to cause electrons to flow in a circuit or
to make reactions go; and the result of energy flow evidenced as heat or temperature
change. In other words there are many forms of energy that can interconvert.
To focus our definitions, we will consider internal energy, U, as that corresponding to:
kinetic energy of atoms and molecules in system, potential energy with regard to an
applied field, and internal energy of molecules in bonds or in vibrations and rotations
We need to sum up all those possible energy changes and then we can use this idea.
However, simpler, since experience shows all energy changes can be described as
heat (q) or work (w) or a combination, which gives the operative First law:
U = q + w
Now need to define the concepts of heat and work
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Sign convention for work:
Positive work - done on system, here compression, lower mass in surroundings [V(h) -]
Negative work - done by system on the surroundings, here expansion to raise mass
In thermodynamics, often more convenient to consider pressure-volume work,
pressure is force per unit area against which the mass moves
w = - ∫ F.dx = - ∫∫ pext dA.dx = - ∫ pext dV NOTE: pext can differ from psys
also have electrical work wel = It, I - current (flow charge), - potential (volts), t – time;
or stretching of materials (e.g. membranes), expanding surfaces (bubbles, balloons)
in biology - have muscle contraction work, heart motion, artery constrict mechanical
cells - mobility (mechanical), charge flow across membranes (electrical, for control
and nerve communication), osmotic (concentration change) – all are forms of work
b. expanding a soap (water) bubble from 1.0 cm to 3.25 cm radius, assume surface
tension is 71.99 Nm-1. ( - area, 4r2, tech. 2-D, 1 vari., factor 2, inner-outer surf.)
w = -∫d = -24(rf2-ri2) = - 8 x 72 Nm-1(3.252-1.02)cm2 x10-4m2/cm2 = -1.73 J
(bubble does work on surroundings, -w)
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Heat, q, is similar, only a process-transitory, causes a change (i.e. temperature)
Transfer of energy due to difference in temperature of system and surroundings
Quantity of heat proportional to T compare system to reservoir (source energy)
Sign: q positive if deposited in system, Tsur ↓, negative if given off from system, Tsur ↑
Electrical work for heating much greater than mechanical (P-V) work done - inefficient
Heat Capacity
Response of system to heat flow is described by heat capacity, depends on material
and on phase (solid, liquid, gas) and temperature, and conditions like constant p,V:
Above is an extensive quantity, so often specified as molar quantity, Cm, units JK-1mol-1
Commonly evaluated at constant P or V, for CPm and CVm – note CV or CP (+)
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Consider diagram for CPm at right for Cl2
The solid phase can be seen as collection of
oscillators (lattice that vibrates) and at very low temps
the spacing becomes greater than kT, not populated, so
cannot take up energy, CPm 0 as T 0
But CPm increases rapidly as kT increase and
excite many lattice vibrations, but discontinuity is seen
as it becomes liquid. Liquid CPm higher since more low
energy vibrations
CPm drops on forming a gas, translations cannot
take up as much energy. Steady increase after this from
putting energy into molecular vibrations (internal states)
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Calorimetry – heat const. V system, dU = dq or U = qV - where w = 0, bomb
calorimeter like previous page 3, reaction in bomb changes T of inner bath, but system
is adiabatic, no energy flow inner to outer, U = 0, C - system response to heat: dq/dT
q = CT where C determined by calibrating, burn known subst. or elect heat: q = It
Text example: p.54 – calibrate calorimeter heat with 10A at 12V for 300s
q = 10A x 12V x 300s = 3.6x104 J A = Cs-1, C.V = J
if calorimeter inc. 5.5 K: C = 3.6x10 J/5.5K = 6.5x103 J/K
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Enthalpy -- Defined as H = U + pV
Like U, H is a state function, H independent of path for change
Virtue is relation to heat at constant pressure (common for chemical processes)
[Consider const. P, dU = ᵭqp – pdV – integrate: Uf - Ui = qp – (pfVf-piVi) or qp=(U+pV)]
dH = dqP or for macro change: H = qP
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ideal: H = U + nRT: Cp = (H/T)p = (U/T)p + nR = CV + nR or Cp -CV = nR (text p.78)
Example: Heat water at 100 C and get vapor formed (boil). If 10 g vaporized (lg) and
the heat of vaporization at 1 atm is qvap,g = 2.27 kJ/g for H2O, what are H and U for
the process (assume ideal gas)?
H = qp = qvap,g .m = 2.27 kJ/g x10.0g = 22.7 kJ
U = H -nRT = 22.7 kJ – (10g/18gmol-1)x8.314JK-1mol-1x373K = 20.9 kJ
DSC analyses are very useful in biochemistry for determining energies of binding of
substrates to biomolecules, and of structure changes (folding)
p.62 text has a nice discussion of DSC methods and sensitivity it achieves
Sample and reference (e.g. solvent) are put in two identical metal holders
Each is heated at a constant rate (T=T0+t, t=time) and the difference in heating current
is difference in heat capacity sample and reference (qp = CpT, T = t, q = qp + qpex)
Cp = qPex/T = qPex/t = Pex/ where Pex - extra power for sample compared to ref.
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Irreversible work, const pext Reversible processes, pext = pint
Above expansions against constant pressure sound “sudden” i.e. release the piston and
it goes up or down irreversibly - depend if pext is < or > pint (fig left) wirrev brown area
Alternative is to have pext = pint and system is at equilibrium, if infinitesimally reduce pext,
system expands, does work, and if then infinitesimally increase p ext can reverse process
such a system stays in equilibrium through change and does reversible work, wrev (right)
wrev = -∫ pdV - where p is no longer a constant, but changes with V (yellow+brn)
Do cycle: Start P1 = Pext, creates V1 at T1, remove weight, get P’ext=P2, expand to V2
suddenly, irreversible, but keep in diathermal container in a bath, so const T1
Now put weight back on, compress back to V1. Consider cycle: U = 0 = qtot +wtot
wtot = -P2(V2-V1) – P1(V1-V2) = -(P2-P1)(V2-V1) wtot > 0 since P2 < P1 (wtot on syst)
Fig 2.9 - red rectangle work (-) 1st step, red plus yellow (+) work 2nd step, wtot = yellow
Arrows indicate which process (compress, expand) happening (sorts signs)
Since U = q + w = 0, then qtot = -wtot and thus qtot < 0 (system loses heat to surr.)
Fig 2.10, both same area, but areas differ in irrev. - one larger one smaller, Fig.2.9
First step, expansion work by system, wrev > wirev - focus on work by system
(but total work in cycle, wrev < wirev, which is fct of sign convention)
Similarly, qtot = -wtot = 0 reversible conditions, require const. T,
if T vary: q≠0, w≠0, case for adiabatic
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Imagine doing the expansion in two steps, to intermediate Px, Px< P1, Px> P2
Look at work, wirev, expansion work by system, 2 step more w (“more” mean more neg.)
w1 + w2 = -Px(Vx-V1) -P2 (V2-Vx) = -(Px-P2)(Vx-V1) -P2 (V2-V1) > -P2 (V2-V1) (neg↑)
Engel - Fig 2.11 -- if more steps, get more rectangles, each touches curve of wrev at top,
(stops at curve, Pext=Pint, equil.) inc. # steps inc. work possible by the system
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Bio example: consider conversion glucose to ethanol
C6H12O6 2C2H5OH + 2CO2
In cell this is facilitated by enzyme and uses ADPATP to store some energy
C6H12O6 +2HPO42- + 2ADP3- 2C2H5OH + 2CO2 +2ATP4-
Overall efficiency of bio reaction – break into multiple steps-- is ~30%
But if done in single step, only work would be pV expansion, wirrev, of CO2, effic~3%
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