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K / K ' the ratio of the forward and reverse adsorption rate constants, is the conven, where K tional adsorption equilibrium constant The second equality in this equation is equivalent to Eq (14106), and indicates that the adsorption equilibrium constant is equal to Henry's constant divided by m, ie, K = klm Since the assumptions upon which it is based are fulfilled at low surface coverage, the Langmuir isotherm is always valid as 0 -+ 0 and as n -+ 0 Even though these assumptions become unrealistic at higher surface coverage, the Langmuir isotherm may provide an approximate overall fit to n vs P data; however, it does not lead to reasonable values form Substituting a = A / n in Eq (14103) gives:

n = 0) to P = P and Il = Il yields:

The second paradox is probably even more troubling My father likened success to a narcotic: It saps the elation of victory, he once said, and deepens the despair of defeat The leader is particularly vulnerable to these highs and lows The leader is the embodiment of the organization s successes and failures (even though he or she may have less direct impact on those successes and failures than many people in the front lines have) Attempting to explain his reasons for stepping down as the Packers coach, Lombardi emphasized that a win was sometimes more of a burden than a loss

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This equation provides the only means for evaluation of spreading pressure The integration may be carried out numerically or graphically with experimental data, or the data may be fit to an equation for an isotherm For example, if the integrand n / P is given by Eq (14107), the Langmuir isotherm, then:

an equation valid for n -+ 0 No equation of state is known that leads to an adsorption isotherm which in general fits experimental data over the entire range of n from zero to full monolayer coverage Isotherms that find practical use are often 3-parameter empirical extensions of the Langmuir isotherm An example is the Toth equation:24

a What is point C called List the characteristics of this point b What happens to a substance at point E if the temperature is increased at constant pressure c Assume point F is at 0 C and 1 atm Describe the changes that would occur when moving directly from point F to point G (still at 0 C) d Solid bismuth is less dense than liquid bismuth How would this change the appearance of the diagram Explain

which reduces to the Langmuir equation for t = 1 When the integrand of Eq (14108) is expressed by the Toth equation and most other 3-parameter equations, its integration requires numerical methods Moreover, the empirical element of such equations often introduces a singularity that makes them behave improperly in the limit as P + 0 Thus for the Toth equation ( t < 1) the second derivative d 2 n / d p 2approaches -cc in this limit, making values of Henry's constant as calculated by this equation too large Nevertheless, the Toth equation finds frequent practical use as an adsorption isotherm However, it is not always suitable, and

When I quit, I knew I d never be back coaching I knew I wouldn t be able to take it again The pressures were so horrible You know, the pressure of losing is bad, awful, because it kills you eventually But the pressure of winning is worse, infinitely worse, because it keeps on torturing you and torturing you and torturing you At Green Bay, I was winning one championship after another, after another, after another I couldn t take it, because I blamed myself, damned myself, whenever they lost a game I couldn t ever forgive myself for a loss, because I felt I d let them down I felt I wouldn t be able to raise myself to the right pitch for the big games, and then I wouldn t be able to raise them to their best effort

Figure 1423 Adsorption isotherm for ethylene on a sieve at 32315 K (50 C) Legend: a experimental data; - - - Henry's law; tion; - - - Langmuir equation n -+0

carbon molecular Toth equa-

.

a number of other adsorption isotherms are in use, as discussed by S U Z U ~ Among them, the ~ ~ ~ Freundlich equation, n $ = - =ap1/fl (P > 1) (141 11) m is a 2-parameter (a and B) isotherm that often successfully correlates experimental data for low and intermediate values of 8

LOMBARDI RULE #10

Engineering, pp 35-51, Elsevier Amsterdam, 1990 Hirata, and H Mori, J Chem Eng Data, vol 27, pp 317-320, 1982

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