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Static Volumetric Methods for Determination of Absorbed Amount of Gases on Clean Solid Surfaces

Z . Knor Institute of Physical Chemistry Czechoslovak Academy of Science Prague. Czechoslovakia

I INTRODUCTION

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258

1 1 . VOLUMETRIC DETERMINATION OF ADSORBED AMOUNT IN STATIC APPARATUS

260
267

I11 APPARATUS REQUIREMENTS WITH REGARD TO ACCURACY OF ADSORPTION MEASUREMENTS

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IV ESTIMATE OF THE VOLUME OF AN ADSORPTION APPARATUS

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272 275 279 287 289 295 297


298

V CONSTRUCTION OF STATIC ADSORPTION APPARATUS FOR VOLUMETRIC MEASUREMENTS


VI . VACUUMSYSTEM

.......................... VII . ADSORPTION VESSEL ....................... VIII . BURETSPACE . . . . . . . . . . . . . . . . . . . . . . . . . . . . I X. RESERVOIRS AND DOSING OF GASES . . . . . . . . . . . . .
X SPECIAL TYPES OF ADSORPTION APPARATUS

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XI SOME GENERAL NOTES ...................... XI1 APPENDIX A Example of the Calibration B Example of Calculation of Amount Adsorbed

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............................... .................. . ....... References ...............................

303 303 305


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I. INTRODUCTION

Z. KNOR

The amount of g a s adsorbed on the surface of solids is one of the fundamental data of adsorption studies. The amount adsorbed can be determined either from p r e s s u r e changes within a certain constant volume-volumetric determination-or more directly from the change of weight of a solid substance (adsorbent)-weight determination-in a static or flow apparatus. In a static apparatus a known amount of g a s is admitted t o the adsorbent in doses, whereas in a flow apparatus the gas flows over the adsorbent for a certain time. In this a r t i c l e we shall deal only with the determination of the amount of adsorbed gas by means of static apparatus . In all our further considerations we shall s t a r t with the fundamental assumption that the studied g a s is adsorbed only on a given adsorbent sample-there is no other source of gas in the apparatus, nor any gas-absorbing parts. This assumption is, of course, only valid for the ideal case. In reality, one only approaches such a state because removal of gas s o u r c e s within the apparatus by perfect degassing can, in turn, give rise to s u r f a c e s which readily adsorb g a s e s during the adsorption experiment itself, e.g., degassed metal p a r t s such a s valves or electrodes of p r e s s u r e gauges or degassed freezing t r a p g l a s s immersed in the cooling liquid during the course of the experiment, etc. Some types of p r e s s u r e gauges have, on the one hand, the prope r t i e s of pumping elements (ionic pumping by ionization p r e s s u r e gauges) and, on the other hand, they can r e l e a s e gases during operation (e.g., ionization p r e s s u r e gauges with hot cathode) o r change the gas phase composition. They can thus influence the course of adsorption. A s a n example [ l - 3 1 the atomization of hydrogen can take place on a hot cathode; hydrogen atoms are then adsorbed by mater i a l s by which molecular hydrogen is not adsorbed a t all. In r e a l situations it is therefore the relative magnitude of these effects which is important: If the surface a r e a of the studied adsorbent is sufficiently l a r g e s o that the amount of g a s captured by it is large compared with the amount of g a s e s released or captured by other p a r t s of the apparatus, then these effects can be neglected. This is the reason, in many instances, it is of advantage to work with evaporated films of materials. Their surface a r e a , in the majority of c a s e s , exceeds many t i m e s the geometric a r e a of the substrate on which the film is deposited. A s mentioned before, perfect degassing of the apparatus brings about not only the condition necessary for preparing clean and defined adsorbent surfaces, but a t the same time it also

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brings about the condition affecting the accuracy and reliability of measurement of amounts of gas adsorbed. The mass balance for adsorption in an ideal case, i.e., when only an interaction between gas and adsorbent surface is involved, i s given by

where vg is the rate of increase of the number of particles in the gas phase over the adsorbent; v, is the rate of addition of gas particles to, and v, the rate of removal of particles from, a given space; V a andvd a r e the r a t e s of adsorption and desorption, respectively. A l l r a t e s can be expressed a s the numbers of particles adsorbed o r transported in 1 second, for example. In a classical static apparatus, beginning from a certain time after the admission of a gas dose, v, = 0. A steady state (vg = 0) is then set up if

because v, = 0 also in case of the classical measurement. In this case, therefore, the extent of surface coverage at a given steady state pressure can be affected only by temperature changes. With flow apparatus where v, * 0 and v, f 0, the condition of the steady state is

s o that the degree of coverage can also be affected by the magnitudes of the r a t e s v, and v2. This advantage of flow apparatus i s more than counterbalanced by a drawback. With the same initial concentration of impurities in the gas phase, the amount of the surface of the adsorbent covered by the impurity can be many times greater in a flow system than in static apparatus because the impurity can accumulate successively. The type of adsorption apparatus to be used is dictated by the following factors.
1. Kind of Adsorbent The kind of adsorbent predetermines the type of adsorption vessel. The surface a r e a of the adsorbent again limits the volume of the whole apparatus.

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2. Kind of Adsorbate The adsorption of g a s e s and vapors having low condensation temp e r a t u r e s brings about a number of complicating factors. It is nece s s a r y to use proper cooling for freezing t r a p s in order that the adsorbent be sufficiently protected against mercury or oil vapors coming from vacuum pumps and a t the same time to prevent condensation of the vapor under study in the t r a p s . In some c a s e s i t is nece s s a r y to keep the whole apparatus a t a temperature higher than that of condensation.
3. Range of P r e s s u r e s in which Adsorption I s Being Studied

With p r e s s u r e s p < 760 t o r r we speak of low-pressure adsorption and in the c a s e of p > 760 t o r r of high-pressure adsorption. So f a r , adsorption on clean surfaces has been studied only at low p r e s s u r e s and therefore attention will be paid only t o this a r e a .

4. Type of Information Desired


Equipment of the apparatus depends on the quantities we a r e to measure. They can be equilibrium and/or steady state amounts adsorbed or desorbed, adsorption and/or desorption kinetics, etc. The type of the adsorption v e s s e l depends, furthermore, on our possible intention t o avail ourselves of some additional method for studying adsorption, such as the measurement of electric conductivity o r of work function of the adsorbent, of infrared spectra of adsorbed p a r ticles, etc. When designing an adsorption apparatus, due r e g a r d must be a l ways paid t o two aspects. Some demands on the apparatus result from the necessity of working with defined surfaces (the use of high vacuum technique); some others are dictated by the sensitivity and accuracy required of the measurements. These two groups of demands often conflict. For example, large glass tube diameters offer the possibility of perfect degassing of the apparatus, but then an apparatus of large volume i m p a i r s the accuracy of determination of the adsorbed amount. It will be necessary, therefore, t o t r y to find the optimum solution in each individual case.
11. VOLUMETRIC DETERMINATION OF ADSORBED AMOUNT IN STATIC APPARATUS

The principle of volumetric determination of the adsorbed amount in a static apparatus consists in the admission of a known amount of

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261

gas-from a known volume of the so-called buret space* filled with gas of a measured pressure-into the adsorption v e s s e l of known volume and in again measuring the p r e s s u r e . The adsorbed amount Na (in moles) is then calculated f r o m

, are the number of moles of g a s in the buret space where N, and N and in the free volume of the adsorption vessel (in the volume not filled with adsorbent), respectively. With the first dose of gas, NA = 0. Symbols with p r i m e s denote numbers of moles in the appropriate volumes after opening the valve separating the buret space f r o m the

FIG. 1. Scheme of simple adsorption apparatus. A , Adsorption vessel; B , buret space; M , pressure gauge; D, dosing system; R , gas reservoir; P , connection to vacuum pump; v, valves.

adsorption v e s s e l (Fig. 1). Symbols without p r i m e s r e f e r to the state p r i o r to the admission of a dose. Mentioned numbers may be equilibrium o r stationary state values o r they may be time dependent. To be able t o determine the adsorbed amount, it is necessary to e x p r e s s the numbers of moles in individual p a r t s of the apparatus by means of the measured quantities: p r e s s u r e , p; volume, V; and temperature, T. At temperatures sufficiently high above the critical temperature o r a t low p r e s s u r e s , the studied g a s can be considered a s an ideal one and the correction accounting for the nonideal behavior [see Eq. (2111 can be neglected.
*Note: The buret space i s that p a r t of the apparatus i n which we measure the amount of gas p r i o r to admission of a dose of gas to the adsorbent.

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Z . KNOR -

Furthermore, i f the whole apparatus has a constant temperature T, then it is possible to write for numbers of moles in individual p a r t s of apparatus (Ni = N A YN,, NA, NA):
N.

Pivi
-

1 - R T

(5)

Here R is the g a s constant, pi is the p r e s s u r e in Vi, and Vi is the volume of the space in question. The adsorbed amount Na is then [see Eq. (l)] a simple function of products PiVi. As far as some p a r t s of the apparatus a r e kept at the temperature differing from other p a r t s (freezing traps, adsorption vessel), we must write f o r the amount of g a s in the buret space o r in the adsorption vessel space

where NTK is number of g a s moles in volume V , of that p a r t of the apparatus which has the temperature TK. In deriving the expression N i = Ni(&, V,, TK, we must now distinguish two cases: 1. The mean free path of g a s molecules* is much less than the diameter of tubes crossing the region of the gradient of temperatures. In this case the p r e s s u r e is the s a m e in the whole apparatus and equals the p r e s s u r e measured by a p r e s s u r e gauge working a t temperature T . Thus we can write for the p a r t kept at TK:
N,,
=-

PivK RTK

and furthermore

where a,

T1/TK.

2. The mean free path of g a s molecules is g r e a t e r than o r equal t o the diameter of tubes crossing the region of temperature gradient. In this case the so-called t h e r m a l transpiration effect (thermomolecular effect [ 5,6]) occurs. Let u s consider two volumes, V, and V,, each i m m e r s e d in a bath
*Note: To estimate the mean free path h (in centimeters), it is possible to use the approximate relation 141 hp = 5 x 10 (cm. t o r r ) with the majority of simple gases.

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263

of different temperature. Depending on the ratio of the diameter of the tube (connecting the volumes and crossing the temperature gradient) and of the length of mean f r e e path, the pressure p1 in volume V, may differ from the pressure pz in volume V,. According to Knudsen [ 5 , 6 ] , we can conceive the microscopic picture of processes in the region of the temperature gradient as follows: A molecule arriving from the side of the higher temperature transfers to the wall a momentum which is greater than that transferred to the wall by a molecule arriving from the side of the lower temperature. According to the action and reaction principle, the momentum retransferred by the wall to molecules and directed toward the higher temperature is greater than the momentum transferred to the molecules in the direction toward the lower temperature. A s a consequence, a flow of molecules from the low-temperature region to the highertemperature region occurs at the wall. Molecules flow through the inner region of the tube back into the lower-temperature volume to compensate the flow along the walls. After a certain time a stationary state of flows in both directions is established.* The extent in which this wall effect operates is in the first place determined by the ratio of the number of mutual collisions of molecules to the number of impacts of molecules on the walls, i.e., by the ratio of the mean f r e e path and the tube diameter. Obviously, the thermal transpiration effect will thus at a given pressure mainly operate with tubes of small diameters. With them the layer of gas flowing along the wall represents a volume which cannot be neglected. In the region of very low p r e s s u r e s (n >> 2r, where n is the mean f r e e path of molecules and r i s the tube radius), a relation can be obtained between pressure p1 in volume V, at temperature T, and pressure pz in volume V, at temperature T,. The relation is derived by considering the number of impacts in a time unit on an a r e a unit of the c r o s s section of the tube passing through the temperature gradient. The number of impacts must be equal in the stationary state from both sides-both from the side of the higher temperature and from that of the lower one-so that p = Tl Tz Pz = pp2

(9)

Equation (9) gives one limiting value of the correction factor P with regard to the thermomolecular effect. The other limiting value (as was seen under l), equals unity.
*Note: These considerations, of c o u r s e , a r e fully valid only provided the molecules rebound from the wall (the s u r f a c e of which is rough) elastically and provided no adsorption o r desorption o c c u r s on walls.

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Z . KNOR

In the transient region of p r e s s u r e s , the t h e r m a l transpiration influences the amount of g a s in individual p a r t s of the apparatus. It must be taken into account either empirically-by calibration of apparatus volumes in the whole range of p r e s s u r e s involved and for each g a s separately [7,8],-or the correction factor P can be calculated by means of the semiempirical Liang equation [9] or its newer modifications. The Liang equation can be written in the form:

P=

Ay2 + By + C G + D d Ay2 + B y + C f i + 1

where y = 2rp, (r is the radius of the tube crossing the temperature gradient and pz is p r e s s u r e measured a t room temperature). Equation (10) formally s u m m a r i z e s t h r e e modifications of the original Liang equation. Modifications differ by the significance and values of the constants A, B, C, and D. According t o Bennett and Tompkins [lo], the constants of Eq. (10) a r e given by the relations: A = af2GZ
B

=pf@

C =O

D=1

(11)

where cy and /3 a r e constants for helium; Q, is the dimensionless factor characterizing the kind of g a s used (for helium = 1); and f is the correction factor having the values: f = 1.0 for 2r < 1.0 cm, and f <1.2 f o r 2r > 1.0 cm. Values of Q, for some g a s e s are given in Table 1. For other g a s e s Q, can be estimated by using the emp i r i c a l equation:
TABLE 1

Values of the Constant @ of the Liang Equation [lo, 2151


Gas
Q

He Ne A2 Kr Xe H2
0 2

1.00 1.30
2.70

3.90
6.41 1.44 2.87

NZ

co
c0 2
C2H4

3.53 3.31
4.52 6.72 2.22

NH3

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265

where d is the diameter of the particular gas molecule in Angstroms, computed from the collision c r o s s section. Constants a and p a r e given by the relations:

= 6.29

- 9.6

T, Bennett and Tompkins verified Eq. (10) with the given constants for cases where T, < T,. Edmonds and Hobson use the same equation a s Bennett and Tompkins, the only difference being that they take D f 1. The former authors showed that Eq. (10) with values of constants given by relations (11) holds exactly only in c a s e s when the regions of different temperatures, separated by a thin diaphragm, a r e connected by an aperture. If volumes at different temperatures a r e connected by a tube, then even relation (9) does not hold exactly, but

/3 = 7.88 (1

-p)

10-'(T2 - T,)

(1 3)

p1 = D&P2 applies. D is an empirical constant which must be determined from the limiting case li >> 2r. For example, Edmonds and Hobson determined for argon D $ 1.1 at temperatures T, = 77.4"K and T, = 295'K in the region of p r e s s u r e s lo-' < p < 60 t o r r . Only by a number of special processes, enabling them to reduce the experimental e r r o r of pressure determination [ll],were they in a position to determine reliably the deviation of value D from 1. The physical meaning of the constant D is related to the different probabilities of the passing through a tube of molecules coming from volumes at different temperatures. According to Takaishi and Sensui [12], the constants of Eq. (10) a r e given by the relations: A = A,T-2
B
=

B,T-l

C = C,T-lh

(16)

where = (T, + T2)/2 and constants A,, B,, and C, for some gases a r e given in Table 2. Values A,, B,, and C, for the other gases can be approximately estimated by means of empirical formulas:
A,, = 1.4 x

lo4 x exp

(0.57d)

(17)

266
TABLE 2 Thermal Transpiration Effect Values of the Constants of Takaishi Equations [121
A, x B, x lo-', Gas grad2*torr-2mm-2 grad.torr-'mm-'
H2 N2
02*

Z. KNOR -

Range of C,, temp., "K grad0.5.torr-0.5mm-0.5


10.6 10-18 (13)b 13 18-20 30 16 14 10 14-673 77-195 90 473-673 4.2-90 20.4-673 77-673 77-673 77-90

CH4

He Ne Ar
Kr

Xe

1.2 12 9 -7 14 1.4-1.6 2.6 11 14 35

8.0 10 16-19 15 1.1-1.2 1.9 8.1 15 41

aValues A, and Bower e obtained only for a narrow range of pre ssure s s o that i t w a s not possible to determine these values more accurately and it was not at all possible to determine C,. bValue C, was obtained by calculation f r o m Eq. (8) for D 4 A [ l l ] .

B, = 5.6 x exp (0.607d)

(18)

c, =-'lo
d

114

where d is the diameter of molecules in Angstroms, computed f r o m the collision c r o s s section. Takaishi and Sensui verified the validity of Eq. (10) in the range of temperatures 77 t o 673K. They used the equation in such a f o r m that they always took p, < pz and T, < T,, so the p r e s s u r e measured at room temperature was considered either as p, o r as p, according to the temperature. So far the older Liang equation (as modified by Bennett and Tompkins) has been more frequently used in the literature. The value of correction factor P, computed f r o m both equations (Bennett-Tompkins and Takaishi-Sensui), does not change much. The p r e s s u r e c o r rection accounting for the thermal transpiration effect can be very high if temperatures T, and T, differ substantially. For instance, for T, = 78"K, T, = 300K is the limit of P in the region of low p r e s s u r e s ( n >> 2r), roughly P = 0.5. In calculating the amount adsorbed, we can then write for item N i a n equation analogous t o Eq. (8):

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267

The magnitude of the correction in calculating gas amounts depends on the ratio of volumes VK which are at different temperatures [see Eq. (20)]. The volumes VK are usually determined by gas calibration at higher pressures, when the thermal transpiration effect does not =1 ) . play any role (PK Insofar a s we work in the region of temperatures o r p r e s s u r e s where the given gas cannot be considered as an ideal one, the nonideal behavior is expressed by correction:

where V, is the volume of free volume of a part of the apparatus,


TABLE! 3

Values of the Constant y for Correction for Nonideal Behavior of Gases [2141
Temp.,

Gas

"K

yx

torr-*
6.6 3.8 6.3 4.2 3.5 2.7 0.8 3.5 1.6 7.1 11.4 3.9

NZ
0 2

co co2
NH3
CH4

Ar

78 90 78 90 90 195 298 237 298 90 78 90

V the volume corresponding with the nonideal gas behavior, and y a constant dependent on the kind of gas and on temperature (Table 3).

111. APPARATUS REQUIREMENTS WITH REGARD TO ACCURACY OF ADSORPTION MEASUREMENTS In volumetric determinations the measured quantities a r e temperature, volume, and pressure. In studying adsorption at low pres-

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s u r e s on clean surfaces, the demands upon thermostating of the whole apparatus a r e not, a s a rule, strict. F r o m the point of view of accuracy of determining the adsorbed amount, it will usually be sufficient to maintain the temperature constant within the limits of 1-2"K, because the relative deviation of temperature 6, is, in this case (in the temperature region T > 100K), of the o r d e r of 6, i 1%. In some particular c a s e s it is, of course, necessary t o maintain a constant temperature of the adsorption vessel with much g r e a t e r accuracy for other reasons (for measurements of electrical conduc tivity of films, etc.). When measuring a t temperatures different from the room temperature, it is mostly assumed that the thermal capacity of gas admitted to the adsorption vessel from a volume kept a t room temperature is negligibly s m a l l and that the proper adsorption p r o c e s s proceeds at the temperature of the wall of the adsorption vessel. It is only in tl?e c a s e of calorimetric measurements a t pressures p > t o r r that heat transfer by the g a s phase can interfere, but, as to the adsorption process proper, it is again assumed that i t is not affected. Often the g a s is admitted to the adsorption vessel s o that it p a s s e s through a cooling o r warming bath before it e n t e r s the adsorption vessel (e.g., [ 13,14,206]). The magnitude of the volume of the apparatus constitutes one of its fundamental p a r a m e t e r s . The adsorbed and/or desorbed amount of gas is determined as a difference of the amount of gas in the g a s phase within the whole free volume of the apparatus before and after adsorption or desorption [see Eq. (4)]. It is therefore obvious that if we are t o measure the adsorbed amount with sufficient accuracy, the amount of g a s in the whole free volume of apparatus must not be too large as compared with the adsorbed or desorbed amount. The e r r o r of determining the amount of g a s is given by the e r r o r in determining the volume and p r e s s u r e . The relative standard deviation of individual measurement of p r e s s u r e 6 is mostly of the order of 6 = 1%. It is possible to r e a c h a reduction of the deviation by a number of steps [11,15-181, which, however, for practical reasons do not come into consideration for adsorption measurements. * The calibration of volumes of individual p a r t s of apparatus is made either by means of liquids [16] (mercury, water) or with the help of a nonadsorbing gas, e. g., helium.
*Note: The e r r o r of absolute p r e s s u r e measurement with any p r e s s u r e gauge is always greater o r , a t best, practically equal to that made when measuring p r e s s u r e with an absolute manometer, against which the given p r e s s u r e gauge was calibrated. Therefore, when measuring at low p r e s s u r e s , the e r r o r i s essentially determined by the e r r o r of the McLeod p r e s s u r e gauge. It i s possible to reduce the e r r o r of individual measurement by repeated readings

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Calibration of volumes by means of liquids and especially of mercury is usually a very precise one and a deviation of only 6 s 0.1% can be easily attained. Calibration with gases consisting of the admission of a known amount of gas into the volume being measured and in the measurement of pressure is not, however, a quite independent method, because we must know the initial volume, e.g., the volume of the McLeod manometer, with the greatest accuracy possible. Provided we know this volume, the amount of gas used for the calibration can be determined by pressure measurement with an e r r o r given essentially by the accuracy of the pressure measurement. Therefore the fundamental calibration of the selected part of apparatus-gas buret, McLeod manometer-is always made by means of a liquid, preferably mercury. In the calibration of further p a r t s of the apparatus by means of gases, it i s suitable that the initial volume Vc be approximately equal to the calibrated volume V, because the e r r o r of calibration is minimal when V = VC, * and that the calibration be made in the region of p r e s s u r e s where the manometer used measures with the least relative e r r o r . There is, of course, the obvious assumption that prior to the admission of gas the calibrated volume must have been evacuated so that the amount of gas in it is negligible compared with the amount of gas admitted.
and by use of the mean value, but an e r r o r in absolute p r e s s u r e i s , in the c a s e of the McLeod p r e s s u r e gauge, given by the e r r o r of determination of its content. It cannot be affected by number of readings, The absolute e r r o r of press u r e determination by a McLeod manometer i s determined by the e r r o r in calibrations of volume o r of diameter of the sealed capillary. The latter error is usually of the o r d e r of units of percent. Calibration of the total volume of a McLeod p r e s s u r e gauge can be made with a much g r e a t e r accuracy. Suitable construction and equipment for accurate reading of the height of mercury column o r that of some other liquid in p r e s s u r e gauges is described in literature [11,15-181. Wote: Let us consider an ideal gas, admitted f r o m a known volume VC (where it was closed under p r e s s u r e pi) into the evacuated volume V. If both volumes have the same temperature, the relation:

v = Vc- P1 -Pi!
Pz holds, where p2 i s the p r e s s u r e measured after equalization of pressures. The standard absolute deviation of V - u v is with the given deviations uvc and up, = opz= up determined by [191

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Z . KNOR

In measuring the adsorbed amount, not only dimensions of the apparatus matter but also the geometric arrangement of the apparatus is important i n some cases. The influence of the geometric arrangement shows itself on the one hand in the so-called layering effect,* and on the other hand in unfavorably affecting the study of adsorption kinetics. The gas inlet to the adsorption vessel should be arranged so a s to render the largest possible surface a r e a (at least the geometric s u r face area) of the adsorbent exposed to the direct impact of gas molecules. This should prevent the successive covering of surface starting from the place of gas inlet (Fig. 2). The planar layering effect (Fig. 2) can simulate some other than the r e a l degree of homogeneous coverage of surface. Thus it can affect the conclusions drawn from the measured dependences of various physical quantities on surface coverage. For instance, dependences of the heat of adsorption, of electric conductivity, or of the work function on surface coverage, etc., can be distorted.

By substitution from Eq. (a) into (b), we a r r i v e at:

The relative deviation (ov,/VC) = 6v, 0.1% and (up/pz) = 6p2 1%. It i s possible t o neglect the f i r s t t e r m on the right side of Eq. (c) with r e g a r d to the second t e r m and the resulting error of determination V is thus really , will given by accuracy of the measurement of pressure. The deviation u then be minimal when -(2VS that is, when

a av

+v 2 + 2VCV) = 0

v = vc

(e)

*Note: Two types of layering effect a r e discussed in the literature: (1)successive permeation of the adsorbate into the bulk of the adsorbent (it proceeds along pores or by direct penetration into the crystallographic lattice) and (2) successive covering of the adsorbent in the surface plane (parts which a r e nearest to the gas inlet are covered first and immediately up to a certain depth of the adsorbent). The f i r s t type of layering effect cannot be eliminated. Our discussion concerns only the planary layering effect (2).

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271

FIG. 2. Scheme of the planar layering effect. 1 , Gas inlet to adsorption vessel; 2 , thin layer of adsorbent; 3 , layers of adsorbate.

the geometric center of a spherical adsorption vessel [21,22] (Fig. 3) or to use the inlet in the form of the Lava1 jet [23-251 (Fig. 3), which causes scattering of molecules to a wider space angle even though still not fully homogeneously. The transport of gas will not essentially affect the equilibrium amount because it will suffice simply to wait long enough until equilibrium is established. When measuring adsorption kinetics, however, it is necessary to fulfill the fundamental condition: the manome t e r used must always be placed so that the pressure being measured at a particular time and the pressure in the adsorption vessel be equal. This can be attained first by placing the manometer in the immediate neighborhood of the adsorption vessel, and also by using Insofar as we a r e interested in questions concerning the degree of surface coverage, it is of advantage, then, to place the gas inlet in

FIG. 3 . Various kinds of gas inlets to the adsorption vessel with spherical symmetry of the adsorbent layer. 1, Gas inlet; 2, connection to vacuum pump; 3, adsorption vessel.

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Z . KNOR

sufficiently wide connecting tubes (Fig. 4)* and by suppressing changes in p r e s s u r e s caused by the operation of the manometer itself.

IV. ESTIMATE OF THE VOLUME O F AN ADSORPTION APPARATUS Now we shall make a rough estimate? of the maximum size of the free volume V, of the apparatus which still allows working with c e r tain desired accuracy, i.e., with a given relative standard deviation of the individual measurement of the total adsorbed amount Na,:

The estimate is made on the basis of the following assumptions: (1) the studied gas behaves as an ideal gas; (2) the studied gas is admitted to the adsorbent in an amount just sufficient for complete monolayer coverage of the adsorbent at equilibrium pressure pe$; (3) the whole apparatus has a constant temperature T. Then it can be written for the adsorbed amount Na,:

*Note: The rate of gas transport Q can be estimated with the help of a graph (Fig. 4) where Q is given in l i t e r s sec units. To compare the r a t e with the adsorption r a t e being measured, we must usually express it in moles sec-i units. The rate of gas transport in these units Q can be calculated from the relation:

Pi -Pz Qr

where p1 - pz is the difference of p r e s s u r e s in t o r r a t ends of the given tube, T is temperature, and R is the gas constant: R = 0.62 x 10 t o r r l i t e r grad- tNote: This estimate does not represent a full analysis of e r r o r s affecting the accuracy of measurement of the adsorbed amount but it s e r v e s as a guide in the construction of a volumetric adsorption apparatus. %Note: The t e r m equilibrium is used in this article, for reasons of conciseness, both in the sense of r e a l thermodynamic equilibrium and, in some instances, of stationary states, i.e., in cases where the given system practically does not change with time without being in thermodynamic equilibrium (e.g., at irreversible chemisorption).

STATIC VOLUMETRIC METHODS

2 73

Diameter of tube in

cm

FIG. 4. Conductance of cylindrical tubes for a i r a t 293K. [Figure taken from S., Dushman, Scientific Foundations of Vacuum Technique (Chapman and Hall, London, 1949): p. 97.1

where N, is the amount of gas admitted to adsorbent and N, is the amount of g a s in the gas phase after establishment of the equilibrium p r e s s u r e pz. The standard deviation a, of the individual determination Na,iS given by [19]:

Substituting from Eq. (22) we have

274 and after rearranging by means of Eq. (22):

Z . KNOR

where 6, = Uv/V, and 6, = u,/T. write

If there is up1 = up,

up, we can

where GP = Up/pe. By further rearrangement we obtain

From Eq. (27) it follows:

If there is 6 2 ,>> 62, + 6$., we get the rough estimate:

For the desired deviation of measurement of the adsorbed amount 6, and the given e r r o r of measurement of pressure bp, Eq. (29) gives , and the amount Na, the relation between the permissible volume V adsorbed at equilibrium pressure Pe at temperature T (Table 4).
TABLE 4 Suitable Volumes of Apparatus for Various Types of Sorbents Surface area, A, om2 103-1 o4 Permissible volume, V, cm3
1 o4

Type of sorbent Film Crushed crystal Filament

lo3
1

lo3
10

6a = 0.05, 6p = 0.02 (Le., 6a = 5%, 6p = 2%), pe = 6.O23.1Oz3 moles.

aV, is the permissible volume estimated with the aid of Eq. (29) f o r lo- torr, and Na = loi5

STATIC VOLUMETRIC METHODS

275

V. CONSTRUCTION OF STATIC ADSORPTION APPARATUS FOR VOLUMETRIC MEASUREMENTS Each apparatus for the study of gas adsorption on solids is composed of four fundamental parts: vacuum (pumping) system, adsorption vessel, buret space, and r e s e r v o i r s with a dosing system, The

Y
FIG. 5. Mercury float valve, (a), Overall scheme: 1, connection to appar-

atus; 2 , connection to apparatus (from this side the value will withstand an overpressure); 3 , connection to mercury reservoir; 4 and 5, ground joint surfaces; 6 . t r a p for grease t r a c e s from valve 8; 7 , capillary for outlet of mercury from trap. (b) Scheme of using mercury float valve for controlled slow admission of gases: capillary K is equipped with a scale f o r setting the mercury level a t a partial overlap of the group joint. (c) Scheme of using a pair of mercury float values a s a dosing device; valves thus connected will withstand overpressure from any side.

TABLE 5 Cutoffs Used in High Vacuum Technique [311

Type Drawbacks Note

Advantages

Construction examples [26, 34, 35, 151, 1521

U -Shaped (mercury) cutoffs

Practically unlimited duraParts filled with mercury canbility; simple construction not be degassed satisfactorily; and operation; they do not presence of mercury vapors reduce pumping rate: no in apparatus; in case of small sorption on p a r t s of cutoffs dimensions they will not withstand high overpressure

[72,153-1551

Mercury ground joint valves

Practically unlimited duraMercury-filled p a r t s cannot be bility; simple manipulation; degassed satisfactorily, diffithey withstand high overcult construction (to function p r e s s u r e ; possibility of well r e q u i r e s faultless ground using as capillary for slow joints, preferably ball-andfeeding of gas; they do not socket 1721 or planary [1531; presence of mercury vapors reduce pumping rate; no in the apparatus danger of sorption

Dry ground valves

Not source of vapors; pracDo not withstand high overpres- It is of advantage tically unlimited durability; sure; relatively difficult to use optically simple manipulation; posconstruction; can be used polished sursibility of using as capillary only f o r separating spaces faces instead of (slow admission of gas); no at p r e s s u r e s p < torr ground surfaces danger of sorption; can be well degassed

[26,34,36,156, 1571

Metal valves

Easy manipulation; withstand high overpressure; can be often used as valve for rough regulation of gas admission; can be well degassed Danger of oxidation (loss of sealing qualities); owing to high costs of materials (Ga), a r e usually constructed i n small dimensions thus causing reduced rate of pumping; necessity of heating (when opening and closing) to a higher temperature (excepting liquid alloys) Owing to easy oxidation, must be filled with melted metal via the capillary in vacuum; amalgam or oxidized layer remains retained at entrance to capillary

Rather difficult construction; limited durability; sorption on walls; in laboratory types usually substantially diminish rate of pumping

[26,29,33, 158-1631

Cutoffs filled with lowmelting I n metals ( Ga, Sn, or alloys; 62% Ga, 25% In, 13% Sn liquid at room temperaturea

Simple construction and manipulation; with a solid metal withstand high overpressure; are of small dimensions; low tension of vapors even at high temperature; can be well degassed

[26,164-167, 2171

aJ. J. Tret'yakov, and Yu. A. Balognev, private information.

278

2 . KNOR

individual p a r t s a r e separated from each other by cutoffs of widely different types (Table 5). The most frequently used cutoffs in adsorption apparatus a r e mercury U-shaped cutoffs o r float valves, cutoffs filled with low melting metals or alloys, and all-metal valves of the Alpert type. For apparatus operating with mercury (with m e r cury diffusion vacuum pump, McLeod monometer, etc.), mercury float valves a r e of greatest advantage (with ball-and-socket or plane ground joint) [72,153] (Fig. 5). They offer some advantages a s compared with conventional U-shaped cutoffs. A ground joint covered with mercury withstands an overpressure of 1 o r more from one side. When two valves a r e connected i n s e r i e s (Fig. 5), they can withstand atmospheric overpressure from both sides; ground joint not covered by mercury makes it possible to admit gases into vacuum slowly by diffusion. Finally, the volume of the apparatus on the side of the ground joint is not affected by the height of mercury level setting.

FIG. 6. Alpert type all-metal valve 1, driver; 2 , diaphragm; 3 , nose; 4 , cup; 5, vacuum leads.

Alperts all-metal valves (e.g., Refs. [26,29,33]) and cutoffs filled with low-melting metals or alloys a r e of advantage for apparatus without mercury vapors (see Fig. 6). Operation of an allmetal valve i s simple and quick. These valves can also be used for slow admission of small amounts of gas. They also withstand even a high overpressure. Their durability, however, is limited. In some cases the presence of a lot of metal, from which the valve is made, acts a s a drawback. Complete degassing of these valves i s difficult and an interaction of gases with the surface of the degassed metal can occasionally occur. Cutoffs filled with low-melting metals o r alloys (for example, see Fig. 7) mostly offer the advantages of very simple construction

STATIC VOLUMETRIC METHODS

279

C.21

(b)

(C)

FIG. 7. Examples of cutoffs filled with low-melting metals and/or alloys

(a) 12121, (b) [165], (c) [1671. 1, Fasteting plug with sealed iron core; 2, lowmelting metal o r alloy; 3 , level-controlling plug with sealed iron core; 4,
heating; 5, asbestos fabric for springing different thermal expansion of glass and iron and f o r preventing mechanical shocks. All operations of these cutoffs are effected by means of external magnets.

and manipulation. If we do not work with an alloy which i s liquid at room temperature, however, it is necessary, to heat the cutoff to an elevated temperature for each operation. This both complicates the work and brings the danger of release of gases from walls. In the forepumping part of the apparatus and sometimes even in the part for preparation of gases-provided they a r e being prepared at high enough p r e s s u r e s (p > 10 tom)-even greased glass cocks, e.g., Ref. [35], can be used. The main difficulty caused by these cocks lies i n the impossibility of degassing them at a n elevated temperature. In the majority of cases the source of gases released into the apparatus volume is not, a s a rule, the vacuum grease itself (the vapor tension of which can be very low) but rather water and gases dissolved or trapped in the grease. When using the greased cocks it is also necessary to reckon with the fact that, even while degassing other parts of the apparatus by heating, the temperature of cocks must as a rule not exceed T & 300K. At higher temperat u r e s grease is soon pressed out of the ground joint. For this reason water-cooled cocks a r e sometimes used [216].
VI. VACUUM SYSTEM

In this article we shall not deal in detail with the fundamentals of vacuum technique. These can be found in the literature [15,16,26-30, 34-36]. Only the basic properties of some currently used pumping elements (Table 6) and pressure gauges (Table 7) w i l l be mentioned.

TABLE 6

Vacuum Pump Properties [16, 26-37]

Type Advantages Drawbacks Note


0.5 -3

Limit of vacuum, tor r Rate of pumping," 1 sec-l

Forevacuum, torr

Construction examples

Mechanical (at 760 torr); 0.1-1 (at tom) Direct pumping from atmospheric pressure; pumps off all kinds of gases Source of oil vapors; after prolonged use (heating of oil) also of lower hydrocarbons

lo-'-

760

(two-

10-~

stage) oil pump

[16, 35, 361 Principle described in Refs. 116,26,27,34361; protection against oil vapors: freezing traps [34,351; copper foil [29, 30,33,38-411; molecular sieves [421; o r ion trap [43,441

Diffusion oil pump


4-20

lo-''
(at
torr)

2.10-'

No movableparts; Source of oil pumps off all vapors; requires foregases; small dimensions; pumping does not restage quire any particular auxiliary equipment

Principle de[26, 29, 34, 36, scribed in Refs. 481 [16,26, 32-36]; protection against oil vapors: freezingtraps [26,29,30, 33,351; copper foil [38-41]; molecular sieves [42,45,471, aluminum oxide [461

3 x 10-1

3-10 ( A lo-*

Mercury lo-* diffusion Pump torr) Same advantages as diffusion oil pump

Source of m e r - Principle de[16,26,34-36, cury vapors; scribed in 29,49,50,57requires foreRefs. 116, 26, 591 pumping stage 32-36] ; protection against mercury vapors: freezing t r a p s [34,35, 49,501; (event. with maintaining constant level of liquid nitrogen [49-561
[16, 26, 34-36, 29,301

10-210-~

N 03

Ion pumping com- 1 0 - l ~ bined with getter Depends on Pumps off all pump congases (but not struction with equal efand matefectiveness); rial and on no contaminakind of gas; tion of atmo? 0.1-50 (at sphere )dry lo- torr) vacuum.)

Requires auxil- Principle dei a r y equipscribed in ment; limited Refs. [16,26, pumping ca29,30, 34-361 ; pacity; pumped- memory effect off gases remain bound in the apparatus

760;

Sorption on activecharcoal o r molecular sieves

lo-?-

10-2-

Depends on Simple construc- Limited pumping Volume t o 20tion and manipcapacity; slow fold g r e a t e r type of sorbent, its ulation; no poldegassing of than the volsorbent; ume of sorbent preparation lution of atmois pumped off pumped ;off and kind of sphere (dry g a s e s remain from atmog a s (event. on vacuum) rate of coolin the apparaspheric p r e s ing the sort u s assembly s u r e to lo- torr p r e s s u r e bent) e.g., 0.1 (at lo- torr) 1611

[16,35, 36, 37, 60, 3 0 , 4 1 , 4 2 , 61-68]

For laboratory-type pumps.

TABLE 7

Pressure Manometer Properties [27,311

Type of manometer

Range of measured pressures, torr Advantages Drawbacks Note

Construction examples

McLeod manometer

10-6-10

Kl 03 Kl

Absolute manometer (calibration not r e quired); great pressure range; simple manipulation; measures total pressure irrespective of gas phase composition

Operates with mercury Principle described [15-18, 69(mercury vapors in Refs. [15,16, 741 must be frozen out; 26,27,34-361; used for calibration of danger of distortion of data owing to other manometers thermomolecular efModification for mea- [75,761 fect [9-121 and posswing tension of sibly due to freezing condensable vapors trap pumping effect) [77-811; operates discontinuously; relatively long time is required for determination of pressure (2-5 min); pressure cannot be automatically r e corded; impossible to measure pressure of condensable vapors without complications

Pirani manometer
[ 94-1 001

10-5-10-2

[15,16, 82-93]

Pj

03

Manometer readings Principle described Possibility of autodepend on composiin Fbfs. [15,16, matic recording manometer reading: tion of gas phase 26,27, 34-361 (not suitable for meareadings depend on Thermal conducsuring pressure in composition of gas tivity analyzers processes accomphase (manometer panied by changes of can be used as analgas phase composiyzer in connection tion); difficulties with with another type of stability of measuring manometer, e.g., with cell and, possibly of MoLeod gauge); not a electronic circuit; source of impurities, operates at higher vapors; will not be temperature of the destroyed by violent filament (100-200C) admission of high pressure Principle described in Refs.
[15,16,26,27, 34-36]

Membrane manometer

10-3-10

Difficult construction Absolute manometer; (particularly for the possibility of automatic recording; range of lower pressures) manometer data do not depend on composition of gas phase; not a source of impurities and vapors; operates at any temperature (if suitably constructed)

[15,16,35, 101-1081

continued

TABLE 7 (continued)

Type of m.mometer Advantages Possibility of automatic recording; absolute manomee t e r ; not source of impurities and vapors Drawbacks

Range of measured pressures, torr Note

Construction examples
[15,16,35, 109-1121

Knudsen manometer

10-7-10-2

Difficult construction; Principle described shock-sensitive; in Refs. [15,16, operates at elevated 26,27,34-361 temperature; in c a s e s when mean f r e e path is shorter than dimension of tubing, then calibration is nonlinear and manometer reading depends, partially, on gas phase composition [151

BayardAlpert manometer

10-10-10-3

Construction [15,16,26,27, 29,34-36,1061 Circuits [29, 106,120,1221351 Modification for high press u r e s (lo-' t o r r ) [33,125,
136-1381

Possibility of automatic recording; wide measuring range down to region of very low pressures; relatively simple manipulation Manometer reading de- Principle described pends on composition in Refs. [15,16,26, of gases; operates 27,34-361; memory mostly with hot catheffect [15,26,33, 1131; can be used ode (1200-2200K) as pumping ele(cracking of hydrocarbons, hydrogen ment (rate of atomization, etc.); pumping depends on kind of gas, for danger of burning the cathode; h a s pumping N, is about 0.1 effect; relatively com- l i t e r s sec-l [BI; plicated construction pumping effect can f o r electronic circuits be suppressed by reduction of emission current [29, 1391; undefined potential of walls can cause change of manometer sensitivity [50,139,1401

continued

TABLE 7 (continued)

Type of manometer Advantages Principle described in [ 1 5 , 1 6 , 2 6 , 2 7 , 34-361; memory effect [ 1 5 , 2 6 , 3 3 ,


1131

Range of measured pressures, torr Drawbacks Note

Construction examples
[15,26,33,36, 141,1421

Ionization gauge with cold emission Possibility of automatic Manometer reading recording; operates depends on g a s at room temperature; quality; requires withstands rougher s o u m e of high voltage (- 2 kV); handling (e.g., sudden p r e s s u r e increase) difficult degassing of massive elecwithout damage to measuring cell; retrodes; h a s pumplatively simple coning effect struction and mmipulation With special construction, possibility of measur ing extremely low pressures (p < lo-'' t o r r ) Principle described in Fkf. [15,16,26, 27,34-361; memory effect [15,26,
33,1131

10-12-10-3

Can be used as pump- [26,36,1431 ing element (cathodes made f r o m Ti)


[26,144,145, 1461

Mass spectrometers

10-'2-10-4

Possibility of automatic Complicated construcrecording; full infortion and manipulamation on composition tion; in some c a s e s of g a s phase; not source difficult outgassing of impurities (can be of a system well degassed; depends, of course, on type of mass spectrometer)

[26, 33, 36, 147-1501

STATIC VOLUMETRIC METHODS

2 87

Apparatus f o r studying adsorption on clean surfaces of solids are mostly pumped with diffusion pumps. This brings the necessity of working with other construction elements (baffles and cold traps) to remove from the gas phase the vapors of liquids used in vacuum pumps (see Table 6) [34,35]. In the adsorption apparatus proper, where mercury cutoffs and/or mercury manometers a r e used, it is necessary to u s e freezing t r a p s . T r a p s protect other p r e s s u r e gauges (ionization, Pirani, and thermocouple p r e s s u r e gauges) and the adsorption vessel against mercury vapors. Freezing t r a p s of

1
c

FIG. 8 . Examples of single freezing t r a p s . 1, Cooling liquid level.

simple constructions are used as a rule (e.g., Fig. 8), where a tube of equal diameter and shape c r o s s e s the region of temperature g r a dient. This simplifies the calculation of the thermal transpiration effect corrections. If we a r e to deal with well-defined surfaces of sorbents, it is necessary to work in the p r e s s u r e region of the so-called ultrahigh t o m ) . Construction of the adsorption apparatus vacuum (p < must therefore permit attaining these low p r e s s u r e s . The degassing of the apparatus a t temperatures of 670-720K must be provided for. Detailed descriptions of experimental equipment and of p r o c e s s e s for attaining very low p r e s s u r e s can be found in the l i t e r a t u r e [16,
26-33].

VII. ADSORPTION VESSEL The shape of the adsorption vessel and i t s equipment depends 011 the land of information we a r e interested in. Vessels can be modified in various ways f o r studying the influence of adsorption on various physical properties of adsorbents. Changes of the weight [31J may

288

Z. KNOR

be followed, and heat of adsorption may be measured calorimetrically [31,168-1701. Furthermore, electric conductivity of the adsorbent [171-1731, work function [31,174-178,183,1841, magnetic properties [31,179], Hall voltage [31,180-1821, diffraction of slow electrons [31,185,186], etc., may be studied in a suitable adsorption vessel. Adsorption vessels for various form of clean surfaces a r e described in another section of this article. The adsorption vessel is constructed s o that ionization and Pirani gauges, as a rule, a r e protected against vapors of liquids from vacuum pumps, liquid manometers, and/or cutoffs by at least two freezing traps. These, after having been degassed by heating, a r e successively immersed into a cooling bath. At first that freezing trap which is located farthest from the adsorption vessel is cooled while the vessel and the r e s t of the apparatus a r e still heated. In the course of the experiment proper it is necessary to keep constant the level of the liquid cooling within the traps. This prevents back release of condensed and/or adsorbed gases. A number of automatic devices have been described in the literature, e.g., Refs. [49-561. As an example, a device [51] can be mentioned for keeping a constant level of liquid nitrogen o r oxygen (Fig. 9). It uses the

FIG. 9. Device for maintaining a constant level of liquefied gases. G , Vessel; Z, rubber stopper for setting rubber diaphragm R to suitable distance from the opening h; T , tube connection to the source of compressed a i r (the tube i s closed when liquid i s driven by p r e s s u r e of gas evaporated in storage Dewar); K , valve used for filling up the gas thermometer, the sensitive element of which is the bulb b; t , soft tightening; D, storage Dewar; r, rubber hose; m , metal tubes.

STATIC VOLUMETRIC METHODS

289

principle of a g a s thermometer filled with atmospheric a i r o r oxygen. The device is prepared for operation by immersion of a thin wall bulb b (Fig. 9) into liquid nitrogen and by filling it with a i r (or oxygen) through valve K, opened for an interval of 2-3 sec. Location and connection of the instrument a r e shown in Fig. 9. A s long a s the bulb b touches the nitrogen level, rubber diaphragm R does not stick to opening h, and nitrogen evaporating from the r e s e r v o i r Dewar vessel leaks into the atmosphere. A drop of the level (by about 4-6 mm) causes the gas to expand from the flask, rubber diaphragm R closes the opening, and the overpressure of evaporated nitrogen pumps liquid nitrogen out of the storage vessel through tubing P until the level again touches the bulb. F o r pumping of the liquid nitrogen, one can use compressed a i r introduced into the tube T. By this adjustment it is possible to diminish further fluctuation of the level. Frequently, an ionization and/or Pirani manometer is connected directly to the adsorption vessel. The f o r m e r is used f o r determining the degree of degassing of the apparatus o r for measuring adsorption a t very low p r e s s u r e s ; the latter for studying adsorption kine tics.

VIII. BURET SPACE Various p r e s s u r e gauges covering the range of p r e s s u r e s one is interested in and possibly a l s o a gas buret a r e usually included in this p a r t of the apparatus. In the study of adsorption on clean surfaces of solids, we need to measure p r e s s u r e s (p < t o r r ) up to p r e s s u r e of 0.1-5 t o r r . Higher p r e s s u r e s a r e used in the calibration of volumes of the apparatus in a region where the thermomolecular effect does not exert any m o r e influence and in the study of physical adsorption, e.g., of Krypton, the saturation p r e s s u r e ps of which, 2 t o r r . Therefore the adsorption apparatus is a t T * 78"K, is ps usually equipped with an ionization manometer of the Bayard-Alpert type, with a Pirani monometer, and a McLeod manometer. It is of advantage t o u s e some type of McLeod p r e s s u r e gauge which enables u s t o m e a s u r e a wide range of p r e s s u r e s (10-6-10 torr). It is thus possible to calibrate not only the other manometers, but also the volumes of the apparatus with a single McLeod manometer. A s an example, we can name the following type [72] (Fig. 10) of the McLeod which, a s compared with other types, offers two principal advantages: (1) the capillary is not deformed when constructing the p r e s s u r e gauge a s is the case with s e v e r a l capillaries connected in one of stepwise changing diameter; and (2) this manometer h a s a

290
f

Z. KNOR

FIG. 10. McLeod manometer for wide range of pressures. 1 , Permanently pumped-off a r m (eventually sealed); 2 , connection to the apparatus; 3 , connection to the mercury reservoir; 4, mercury U-cutoff closing the pumped-off a r m from undesirable admission of gas when measuring; 5 , capillary for the delayed outflow of mercury (delay in the mercury outflow gives sufficient time for adjusting the mercury level in the manometer between repeated readings).

minimum volume for the given range of p r e s s u r e s . The relation: P =m h , can be used for p r e s s u r e determination with this p r e s s u r e gauge, where K is a constant f o r the narrow and/or wide capillary (Fig. lo), h, the difference of heights of mercury levels in the comparing and measuring (sealed) capillaries, and h, the distance of mercury level

292

Z. KNOR

for the wide capillary; V, is the total manometer volume from m a r k a, V, the manometer volume from m a r k b, V, the volume of the tube and sealed capillary c , and rl and r2 the radii of the narrow and wide capillary, respectively. An ionization gauge of the Bayard-Alpert type [15,16,26-361 is most frequently used f o r measuring the lowest p r e s s u r e s , both in the determination of the degree of degassing the apparatus and in the study of adsorption a t lowest surface coverages. To minimize influencing the p r e s s u r e and chemical composition of the g a s phase by the manometer itself, it is customary to use a cathode covered with a layer of lanthanum hexaboride. The cathode then emits electrons a t lower temperatures and is sufficiently stabile [ 2271, Commercial

2 113

FIG. 11. Bayard-Alpert ionization p r e s s u r e gauge. (a) Commercial type; (b) construction used in our laboratory. 1, Cathode heated by electric current; 2 , grid; 3 , collector; 4, lead to the conductive coating of inner gauge walls.

ionization manometers mostly have the leads for a l l electrodes in one socket (Fig. 11). If the p r e s s u r e gauge is homemade, it is preferable to divide the leads among s e v e r a l joints. Repairs such as
By substituting from Eq. (e) into (d), e.g., for hi and finding

(i.e., the condition for minimum X at a given hi) we obtain

that is,

STATIC VOLUMETRIC METHODS

293

b fi

FIG. 12. Scheme of the electric circuit for ionization guage operation. IoM, Ionization gauge; E, , stabilized source f o r heating the cathode (storage battery); G , source of grid voltage; C , source of collector voltage; A,, measuring instrument for monitoring emission current; A , , instrument f o r measuring cathode heating current; A , direct current amplifier for measuring ionic current. Electron emission current i s usually of the o r d e r of 10-6-10-3 A. Low emission current decreases the pump effect of the gauge.

changing the cathode, collector, etc., a r e then easier (Fig. 11). A stabilized source or batteries and accumulators can be used to run the gauge. Typical values [16,26,33] of voltages used a r e given in Fig. 1 2 . The relation between ionic c u r r e n t i, and emission c u r r e n t i- is given by

where the constant k has a value dependent on the geometric arrangement of the electrodes and on the kind of gas. The value of constant k is usually of the o r d e r of k = 10 torr-I and is determined by calibration, e.g., by means of the McLeod monometer. To eliminate the influence of the undefined potentials of manometer walls [ 50,139,1401, it is of advantage to cover them on the inside with a conducting layer, e.g., 218Sn0, or 50Pt. The layer is then grounded. Thermoconductive (resistance o r thermocouple cell) p r e s s u r e gauges a r e used for following adsorption kinetics and, particularly, for measuring p r e s s u r e s in the range of 10A5-10 t o r r in apparatus operating with the so-called dry vacuum [ 261, i.e., without using liquids either in vacuum pumps or in manometers [15,16,26,34-361. The main problem with these gauges is the stability of their reading. Stabilization of the properties of these manometers is usually effected by heating them in low p r e s s u r e s (0.1 t o r r ) of air at a higher

294

Z . KNOR

2
/

FIG. 13. Pirani gauge. 1, Heating current supply; 2 , connection to apparatus; 3 , spiral stretching the filament 4; 5 , supporting rod.

temperature (8001000K) than that of the measurement. Resistance manometers a r e most frequently used (e.g., Fig. 13). The filament or s t r i p of these manometers is usually made from tungsten or nickel from 0.001 to 0.005 cm thick. In the course of measurement the filament temperature usually amounts to 42O-47O0K, whereas the jacket temperature is 273K o r lower. The filament forms one branch of the Wheatstone bridge and pressure is measured: (1)at a constant intensity of current passing through the bridge (in this case the deviation of the zero instrument of the bridge i s calibrated as a function of pressure); (2) at a constant voltage on the bridge [in which case calibration is made as in (l)]; (3) at a constant temperature of the filament (in this case one calibrates the voltage required to establish the equilibrium of the bridge a s a function of pressure. The last way is particularly advantageous, because in this case the calibration curve is least steep [219] and enables u s to measure more precisely over a greater range of p r e s s u r e s than with the the two other ways. To attain a greater stability, it is of advantage to use symmetrical connection of two equal thermoconductive manome t e r s in the bridge. One manometer serves for measurement and the other (a sealed one) for comparison, both being immersed in the same thermostated bath [ 151. When using a McLeod gauge for calibration of the other manometers, it is necessary t o pay due attention to the pumping effect of the mercury drag from the McLeod gauge [77-811into the freezing traps. An e r r o r caused by this effect can run up to 50-200% of the pressure reading, depending on the gas and diameter of the tubing [77-811. It is advantageous to eliminate the influence of the mentioned effect by suitable experimental arrangement rather than by

STATIC VOLUMETRIC METHODS

295

theoretical calculation [77-801. We can use a narrow tube supplying mercury from the reservoir to the gauge bulb and separate the gauge from freezing t r a p s by means of a nonlubricated ground joint 771. It is also advisable to cool the part of the tube which connects the manometer to freezing traps and to the mercury reservoir down to the temperature of solid CO, [78] or to cool the whole gauge down to 273K [81].

IX. RESERVOIRS AND DOSING OF GASES

Very clean gases suitable for adsorption studies on clean solid surfaces are commercially available usually in the form of sealed glass ampules containing gas under a pressure close to the atmo-

FIG. 14. G l a s s b r e a k seals. 1, I r o n c o r e s e a l e d in g l a s s , s e r v i n g to b r e a k the thin-walled bulb 3 o r tip 4; 2 , a s b e s t o s fabric.

spheric one. Glass break seals [26] (Fig. 14) a r e used for admission of gas into the apparatus. Gas then passes through a dosing device. Most frequently, a system of two or three cutoffs enables one to admit a certain amount of gas into the buret space. The gas volume is either directly measured o r only estimated. Dosing can be also done in such a way that a s e r i e s of ampules is connected to the apparatus, each ampule containing an amount of gas corresponding to 1 dose. This is of advantage especially in cases of condensable vapors (i.e., of gases condensing at room temperature) and in cases when we cannot use other types of valves [23,205,220]. Examples of simple dosing devices can be found in the literature 72,187-189,2281 (e.g., Figs. 5 and 15). A great variety of cutoff types can be applied for dosing gases. Diffusion of gases through certain solids (Table 8) can be used for slow admission of gases into the apparatus and their simultaneous cleaning. The admission of gas is usually effected by means of a tube made of a given solid and heated either by direct passing of electric current [142,194,195] or

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/3 I
FIG. 15. Simple dosing system. 1 , Connection to the gas reservoir; 2 , Connection to the apparatus; 3 , connection to the mercury reservoir. Capillary 4 retards flow of mercury from U-cutoff s o that it i s possible to admit gas from the reservoir to the space between both cutoffs and then to admit only the trapped gas into the apparatus. Hi, Starting position of mercury level; H,, position of mercury level when admitting gas to the dosing volume between both cutoffs. Mercury, flowing out of U-cutoff, raises the level from position H, s o that i t closes the reservoir before the U-cutoff opens.

by an external heater. The latter is mostly made of Nichrome wire wound around the outside of a v e s s e l surrounding the given tube [190] or, in c a s e of higher temperatures, fastened on wire (tungsten) catches or c e r a m i c s within the vessel in the immediate proximity of the tube [27,197,198]. Connection of quartz tubes to the apparatus is effected by means of graded s e a l glass. In the c a s e of metal tubes a tube from Kovar is used to which the respective metal (Pd, Ni, or Ag) is soldered by silver o r gold, and the Kovar metal tube is in turn connected via Kovar g l a s s to the apparatus proper, When studying adsorption kinetics, w e sometimes meet with the requirement of measuring a t a constant g a s p r e s s u r e over the adsorbent. Constant p r e s s u r e over the adsorbent can be secured in

STATIC VOLUMETRIC METHODS


TABLE 8

297

Purification of G a s e s by Diffusion through Solids [311


Wall

thickness,
Gas

Temp.,
O K

Solid
Pd

cm

Purity
1 : 1 0 ' 0 1:106

Ref

H2, D z
0 2

N i
Ag

0.08 0.01
0.03
0.03

400-700 400-600 800-1000

[26, 57, 190, 1911 [26,57, 192-1961 11981


a

N Z
He

Fe
SiO,

< 1020

10:106 (H2); 1:106

126, 1971

w,
'1. I.

0 2 7

co, cod

Nz,

Tret'yakov, private information.

two ways: (1) by admitting gas through a valve automatically controlled by the respective pressure gauge [ 199-2011; (2) by attaching a calibrated volume compensator (essentially a gas buret) to the buret space [202-204,2121. In some c a s e s it is of interest to measure not only the amount adsorbed, but also the amount of gas which can desorb under the given conditions. In such an instance the apparatus can be constructed so a s t o enable u s to repump gas from the adsorption vessel to the calibrated volume by means of some pump (diffusion vacuum pump [24,25], Toepler pump [202]). If a diffusion vacuum pump is used, it itself forms a part of the calibrated volume, and the amount pumped off is measured after this volume including the pump has been separated from the adsorption vessel; the pump is first switched off. The amount desorbed can be also measured without modifying the adsorption apparatus by way of successive desorption steps from the vessel into the buret space which first had been pumped off, i.e., by successive lowering of the equilibrium pressure.

X. SPECIAL TYPES OF ADSORPTION APPARATUS

When studying condensable gases, it is necessary to work under conditions which will prevent condensation within the apparatus proper [23,31,205]. In some c a s e s one must heat the whole apparatus to a higher temperature. Therefore, freezing traps and p a r t s involving the use of mercury cannot be used. However, one can take

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advantage of the easy condensation f o r dosing and gas handling purposes either by cooling a p a r t of the r e s e r v o i r down t o a given temperature and thus setting the p r e s s u r e in the r e s e r v o i r or by measuring the amount of vapors admitted t o the apparatus proper from the amount of liquid evaporated from the calibrated capillary. The last way is especially advantageous in measurements requiring the maintenance of constant p r e s s u r e , e.g., when measuring adsorption isobars, capillary condensation, etc. F o r such c a s e s it is sufficient merely to maintain the liquid a t a suitable temperature corresponding t o the required equilibrium p r e s s u r e . XI. SOME GENERAL NOTES Every apparatus f o r studying adsorption of gases on clean s u r f a c e s of solids should, in principle, be an ultrahigh vacuum apparatus. It is therefore necessary, in working it, to observe the appropriate construction principles and working p r o c e s s e s (baking the whole apparatus for s e v e r a l days under continuous pumping, etc.). F r o m these p r o c e s s e s t h e r e follows a number of requirements touching on the construction elements of apparatus to which due regard must be paid. Apparatus used for studying adsorption of g a s e s on clean surfaces as described i n the literature a r e constructed either vertically or horizontally. To heat them we use, in the first case, heating tapes made of g l a s s fabric; in the second case, it is possible t o construct ovens with relative ease. Examples of apparatus f o r the study of adsorption of g a s e s at low p r e s s u r e s , e.g., on films, can be found in the literature [13,14,25,26,170,171,177,179,201,202,204-2131 (Fig. 16, 17, and 18). The construction principles of volumetric apparatus a r e general and valid for designing apparatus suitable f o r studying adsorption on adsorbents of various types: on films, crushed crystals, and filaments. Static volumetric measurements on filaments were made, SO far, only in the very beginning of r e s e a r c h of adsorption of gases on clean surfaces of metals (Roberts classical experiments) [229] in the 1930s. However, fundamental difficulties which would hinder further pursuit of the r e s e a r c h do not exist. One would, of course, update the equipment, such a s replacing grease-lubricated cocks with all-metal valves o r cutoffs filled with low-melting metals, etc. But it is easily understood that, in view of the s m a l l surface of filament, the requirements on both the vacuum and the minimization of the free volume of the apparatus increase, With static volumetric apparatus, it is possible to study both

STATIC VOLUMETRIC METHODS

299

FIG. 16. Scheme of the adsorption apparatus [1771. 1, Mechanical pump; 2, vessel with active charcoal cooled by liquid nitrogen after degassing (about 3 h r s a t 600K) [61); 3 , single stage mercury diffusion pump; 4, McLeod manom e t e r [721; 5 , Bayard-Alpert ionization gauge; 6, Pirani gauge; adsorption vessel; 8 and 9 , cold traps; 10 and 11, mercury float valves [721; 12, r e s e r voir; 13, semiautomatic dosing system 1721; 14 and 15, vessels with sodium azide and potassium permanganate, respectively; 1 6 , 1 7 , and 18, protection from fluidization of powders and active charcoal; 19, mercury cutoffs; 20, palladium thimble for purification of hydrogen; 21, freezing t r a p for dosing and purification of xenon; 2 2 , xenon reservoir; greased stopcocks. P a r t s of the apparatus framed by dashed lines a r e baked out during outgasing by heating tapes. Vacuum up to lo- torr can be obtained. [Figure taken from Z . Knor, and V. Ponec, Collection Czech. C h e w . Commun., 31, 1172, (1966).1

0,

chemisorption and physical adsorption by measuring adsorption isotherms, capillary condensation, adsorption isobars, and isosteres. * When measuring capillary condensation, which is one of the meth*Note: Adsorption isotherm i s the dependence of adsorbed amount on p r e s s u r e at a constant temperature; adsorption isobar is the dependence of adsorbed amount on temperature at a constant p r e s s u r e ; and adsorption isos t e r e is the dependence of p r e s s u r e over the adsorbed layer on temperature at a constant amount adsorbed.

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Valve-

FIG. 17. An ultrahigh vacuum system [2301 used f o r studying the reaction of a gas with a clean metal film. This system is constructed from glass and metal and can be heated to a high temperature. Ultrahigh vacuum 10-9-10-i0 t o r r can be obtained. [Figure taken from R. W. Roberts and L. E. St. P i e r r e , Science 147, 1529 (1965).1

ods of studying the porosity of a given substance, a further requirement joins those already mentioned. With sorbents exhibiting a hyst e r e s i s loop* in their isotherms, the pressure of gas, in the adsorption vessel when measuring a given point of the branch of isotherm, must not exceed at individual doses the value corresponding to the simple expansion of gas from the buret space into the adsorption vessel at the f i r s t dose, used to reach this point.. This requirement is equivalent to the requirement of measuring each point of the isotherm at a constant pressure for the total time necessary to reach equilibrium. Fig. 19 illustrates an apparatus for the study of porosity of samples with small surfaces by means of adsorption of isopentane at
*Note: In cases where, at higher pressures, the adsorption and desorption curves do not coincide into a single curve, we speak of a hysteresis loop.

STATIC VOLUMETRIC METHODS

301

FIG. 18. Adsorption apparatus pumped off by oil diffusion vacuum pump. 1, Mechanical vacuum pump; 2, reservoir of forepumping stage; 3 , oil diffusion vacuum pump; 4, freezing t r a p cooled with liquid nitrogen; 5, ionization gauge; 6 and 10, titanium getterion pumps; 7 , Bayard-Alpert ionization gauge; 8 and 9, adsorption vessels; 11 and 13, Pirani gauges; 12, reservoir; 14, palladium thimble for purification of hydrogen; 15-23, cutoffs filled with tin and/or GaIn-Sn alloy; 24, dosing volume. The appartus w o r k s as the one in Fig. 17. (Figure taken from Ref. [2311, p. 50.)

201K [223]. For studying capillary condensation, isopentane or some other gas can be used which is liquid at the temperature of adsorption and also has other suitable properties. For example, in the case of samples with a small surface a r e a in an apparatus of great volume, a gas whose tension is sufficiently low at the temperature of adsorption should be used. However, the gas must not also react chemically with the adsorbent. For example, isopentane cannot be used in case of clean surfaces of metals because it decomposes on their surfaces. There a r e also similar limitations (low saturation pressure, inertness) in the use of gases for determination of small surface a r e a s

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14

FIG, 19. Scheme of the adsorption appartus for studying capillary condensation on small surfaces. 1, Adsorption vessel with sample; 2 , tube to the r e s e r voir with isopentane; 3 , freezing trap; 4-8, mercury float valves; 9 and 1 0 , McLeod manometers; 11, cryostat; 12, connection to dosing of isopentane; 13 and 14,connection to vacuum pump. (Figure taken from Nabokov e t al. 12231.)

(e.g., of ethane at 9O"L [220], ethylene at 78 and 90K [221], butane at 157K [221]). Therefore, inert gases such as krypton (at 78K) [206, 20'7,224,2251 and xenon (at 78-90K) [206,207,224,225] a r e used in these instances, particularly with metals. Direct measurement of adsorption isosteres is often very advantageous for both experimental reasons (adsorption equilibrium is reached readily) and reasons of further treatment of the measured results. Direct measurement of isosteres offer a determination of isosteric heat and entropy of adsorption [ 2261. Adsorption isosteres can be measured in the simplest way if, in the course of measuring the isoster the amount of gas over the adsorption layer in the gas phase is negligible as compared with the amount adsorbed. Then we can assume with sufficient reliability that the adsorbed amount does not change during the measurement. This condition c2n be fulfilled either by diminishing the free volume of the apparatus o r by lowering

STATIC VOLUMETRIC METHODS

_. .

303

the pressure at which adsorption is studied. The former way does not, a s a rule, come into consideration with ultrahigh vacuum apparatus, but the latter way has been used for studying adsorption on evaporated films [226]. The main advantage of the static volumetric apparatus lies in the possibility of a relatively simple combination of the measurements with other methods for studying adsorption. In static apparatus it is possible to measure both small and large adsorbed amounts of gases -irrespective of the rate of process of adsorption-and the rate of adsorption. It is for these reasons that the static apparatus is the most universal type for determination of the adsorbed amount of gases.

XII. APPENDIX
A. Example of the Calibration

As can be seen from Eq. (ZO), the volumes of individual parts of the apparatus must be known for the determination of the adsorbed volume. Let u s take, for our example, a simple apparatus (Fig. 20) and the respective volumes will then be:
G

FIG. 20. Scheme of simple adsorption appartus. V1, V,, and Vg, valves; T , freezing traps; A , adsorption vessel; M , manometer; G , inlet of gases; P, connection to vacuum pumps.

V, = volume of the part of buret space having the temperature T 300K VBi = volume of those parts of fre,ezing traps which a r e immersed in a cooling bath with temperature Tc

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V v = volume of the p a r t of the adsorption vessel space with the temperature T 300K Vvi = volume of those p a r t s of freezing t r a p s in the adsorption vessel space which are i m m e r s e d in a cooling bath with temperature Tc Vva = volume of the adsorption vessel immersed in a bath of temp e r a t u r e Ta VM = volume of McLeod gauge, the walls of which have a temperature of T 300K All the volumes mentioned can be determined by calibration either by weighting the liquid-mercury o r water-which fill the given volume; or, more comfortably, by using g a s e s (excepting f o r the volume VM)which do not adsorb on the walls of the apparatus (e.g., H2, He for all-glass apparatus). Calibration is effected at p r e s s u r e s 10-1 < p < 10 t o r r f o r apparatus made of tubes of 1.0-2.0 c m in diameter, i.e., in a p r e s s u r e range where it is certain that the t h e r m a l transpiration effect will have no significance. The volume of the McLeod gauge is, a s a rule, known to u s with sufficient accuracy; we can therefore u s e it f o r calibration of other volumes. Gas is closed in the McLeod gauge under p r e s s u r e p1 and the remaining apparatus is pumped off to p r e s s u r e p << p1 (10- < p < t o r r will usually do). Then the amount of g a s (p,VM) is admitted into the buret space without the freezing t r a p s being immersed in the cooling liquid, SO that we can write

where pz is the p r e s s u r e established in the whole buret space after g a s had been expanded from the McLeod gauge. The freezing t r a p s are then i m m e r s e d in the cooling bath, and the p r e s s u r e pBis measured. In this case,

will hold. F r o m Eq. ( A l ) and (A2) the unknown volumes VB and VBi a r e computed by simple algebra. A quite analogous procedure is also followed in calibrating Vv, Vv,, and Vv,. Volume (V, + vBi) can be used for this calibration without the immersion of the freezing t r a p s in the buret space in cooling baths. Of course, the volume (V, + VBi)must be determined with sufficient accuracy. To approach the condition of minimum e r r o r , the calibrated volume must not be too great as compared with the vol-

STATIC VOLUMETRIC METHODS

305

urne known. With the calibration we obtain a system of equations:

where pi7 pi, pg, and p i have a n analogous meaning as pi in Eq. (Al) and (A2). Unknown volumes Vv, Vvi , and Vva can be computed from Eq. (A3) - (A5).
B. Example of Calculation of Amount Adsorbed

In t h i s example the simple apparatus (Fig. 20) will again be considered. A s the freezing t r a p s both in the buret space and in the region of the adsorption vessel a r e made from tubes of the s a m e diameter, it will do to compute a single correction factor P, (p) for them from Eq. (10); individually, of course, for each gas studied. F o r the adsorption vessel it is necessary to calculate the correction factor for the given diameter of the tube crossing the temperature gradient. This is to be done for all temperatures encountered in the course of studying the adsorption. F o r a chosen temperature and g a s we denote the factor a s Pa(p). The ratio of temperatures T/Tc will be denoted a s ac, and T/T, = a,. The p r e s s u r e measured by the manometer in the buret space p r i o r to the admission of a dose of g a s into the adsorption vessel space is p1 and simultaneously the p r e s s u r e in the adsorption vessel space is pz (at the f i r s t dose of gas pz = 0). Furthermore, i f we denote the equilibrium p r e s s u r e which is established after the two spaces had been connected a s p3, then the amount of g a s Na adsorbed at the dose i s given by

E and where P&is the value of correction factor Pc a t p r e s s u r e pl, P P : the values of these factors at p r e s s u r e pz7and Pg and Pg the values a t p r e s s u r e p3. In current measurement i t is of advantage to

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construct graphs for each gas and each temperature of adsorption vessel and of freezing t r a p s such that:

pv = f(p)
RT both for the buret space where

and for the adsorption vessel space where

The adsorbed amount is then determined graphically. Dependences (A7 are represented in bilogarithmic coordinates by lines only moderately curved, approximating straight lines, s o that the reading of values is sufficiently accurate in the whole range of p r e s s u r e s .

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307

[13] R. Suhrmann, A. Hermann, and G. Wedler, 2.Physik. Chem. (Frankfurt), 35, 155 (1962). [14] Y. Mizushima, J . Phys. Soc. Jafian, 15, 1614 (1960). 1151 J. H. Leck, Pressure Measurement in Vacuum Systems, The Institute of Physics, London, 1957. [ 161 S. Dushman, Scientifique Foundations of Vacuum Technique (J. M. Lafferty, ed.), Wiley, New York, 1962. [17] C. G. J. Jansen and A. Venema, Vacuum, 9, 219 (1959). [18] H. H. Podgurski and F. N. Davis, Vacuum, 10, 377 (1960). [19] H. D. Young, Statistzcal Treatment of Experimental Data, McGraw-Hill, New York, 1962. [20] D. Brennan and J. M. Jackson, Proc. Chem. Soc., 1963, 375. [21] D. 0. Hayward, N. Taylor, and F. C. Tompkins, Discussions Faraday Soc., 1966, in press. [22] G. Wedler and M. Fouad, 2. Physik. Chem. (Frankfurt),40, 12 (1964). [23] R. Suhrmann, J. M. H er r as , L. V. de H erras, and G. Wedler, Ber. Bunsenges., 68, 511 (1964). [24] G. Wedler, 2.Physik. Chem. (Frankfurt), 24, 73 (1960). [25] R. Suhrmann, H. J. Busse, and G. Wedler, 2.Physik. Chem. (Frankfurt), 47, 1 (1965). [26] R. W. Roberts and T. A. Vanderslice, Ultrahigh Vacuum, P r e n tice-Hall, Englewood Cliffs, N.J., 1964. [27] G. Lewin, Fundamentals of Vucuum Scimce and Technology, McGraw-Hill, New York, 1965. [28] G. Ehrlich, Advan. Catalysis, 14, 256, (1964). [29] D. Alpert, Handbuch d e r Physik, Vol. 12 (S. Flugge, ed.), Springer, Berlin, 1958, p. 609. [30] P. A . Redhead, J . P. Hobson, and E. V. Kornelsen, Aduanc. Electron. Electron Phys., 17, 323 (1962). [31] V . Ponec, Z. Knor, and S. Cerny, Adsorpce nu pevngch lcitkdch (Adsorption an Solzds), SNTL, Prague, 1966, in p r e s s . [32] H. A. Steinhertz and P. A. Redhead, S c i . Am., 206, 2 (1962). [33] J . M. Lafferty and T. A. Vanderslice, Proc. IRE, 49, 1136 (1961). [ 341 J. Groszkowski, Technologia Wysokieg Prdzni (High Vacuum Technology), Panstwowe Wydawnictwa Techniczne, Warsaw, 1955; Russian translation, IIL, Moscow, 1957. [35] G. C. Monch, Neues und Bewahrles uus d e r Ho~hz)akuumterhnik, VEB W. Knapp, Halle/Saale, 1959. 1361 A. B. Barrington, High Vacuum Engineering, Prentice-Hall, Englewood Cliffs, N.J., 1963. [37] N. Beecher and N. P. Hnilicka, 5th National Symposium on Vacuum Technology of the AVS, San Francisco, 1958.

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