of - nasa · all concentrations are irz; teres qf solute unless noteo,.. -b = sulvent concn. ... in...
TRANSCRIPT
I' i I ,
NASA Grant NGR-21-003-053
Semiannual Status Report
November 1, 1967 to April 30, 1968
t
Department of Chemical Engineering Institute of Molecular Physics
University of Maryland College Park, Maryland
GPO PRICE $
CFSTl PRICEtS) S
Microfiche (MF)
ff 653 July65 .
https://ntrs.nasa.gov/search.jsp?R=19680016891 2020-05-19T16:56:06+00:00Z
Statement of Work
The purpose of t h i s program i s t o compile and i n i t i a l l y e v a l u a t e d i f f u s i v i t y and v i s c o s i t y d a t a on g a s , l i q u i d , s o l i d and t u r b u l e n t flow systems. The program has been i n ope ra t ion f o r two and one h a l f y e a r s . cussed s e p a r a t e l y i n the fol lowing s e c t i o n s .
Progress i n t h e var ious a r e a s of t h e program is d i s -
Binary Liquid D i f f u s i v i t i e s
One of t h e p r i n c i p l e accomplishments t o d a t e has been the completion of a computerized d a t a logging system and w i t h a p rov i s ion f o r s e l e c t i v e r e t r i e v a l of da t a . Concurrently w i t h t h e r e s o l u t i o n of t h i s d a t a logging and re t r ieval system a complete program of review procedures has been worked out t o permit t h e c r i t i c a l eva lua t ion of molecular d i f f u s i o n c o e f f i c i e n t s on a sys temat ic b a s i s . The e f f o r t s
, t o date have centered excluaively on t h e molecular d i f f u s i o n c o e f f i - c i e n t , however, it should be r e a l i z e d t h a t t h e logging and re t r ieval system will work equa l ly w e l l f o r v i s c o s i t y da t a .
The d a t a logging and retrieval system may be c h a r a c t e r i z e d b r i e f l y by t h e fol lowing po in t s : c o d i f i e d t o t h e system used by the Purdue Thermophysical P r o p e r t i e s Review Center and the fol lowing da ta are logged f o r each system. (1) s o l u t e and so lvent des igna t ion and name, (2) temperature , (3) s o l u t e concen t r a t ion , ( 4 ) d i f f u s i o n c o e f f i c i e n t , (5) type of d i f f u - s i o n c o e f f i c i e n t and method of measurement, (6) p r e c i s i o n , (7) l i t - e r a t u r e r e fe rence f o r t h e d i f f u s i o n c o e f f i c i e n t , (8) rshe v i s c o s i t y v a l u e f o r t h e system, and (9) t h e r e f e r e n c e f o r :he v i s c o s i t y va lue . The above are d a t a va lues from the l i t e r a c u r e . ou t precedes each Table t o g ive d i r e c t i o n s f o r use. The r e t r i e v a l system developed permi ts recall of sny scored di-rta on t h e b a s i s o f : so lven t of s o l u t e name, temperature , t he d i f f u s i o n caeff:cient a t i n f i n i t e d i l u t i o n , a p a r t i c u l a r KYP: of c i f f u s i o n c o e f f l c i e r L t o r a p a r t i c u l a r exper,mental method, a pdr t icu1Lr l i t e r a t u r e r e f e r e n c e , o r f i n a l l y r e fe rence 5y a g iven year. Ti3cs, once t h e avzLlrSle experimenral d a t a it completely logged, we a r e i n a posi:lor. :c re t r ieve d a t a by s o l u t e , s o l v e n t , or sysrems and =:&us ncre : r z e ~ - t i v e l y begin the process o r c r i t i c a l eva lua t ion and ae i zcz ion of most probable va lues . r e t r i e v e d i n the same manner, on demand. procedures and a t y p i c a l p r in tou t i s appended t o t h i s b r i e f r epe rc .
t he so lven t and s o l u t e names are
An informat ion p r i n t -
- c
Thel'approved" va iues cap. rhen be l o ~ g e i and A sample of the indexlng
A t t h e p re sen t t i m e we have most of the organLc systems
W e have no t as y e t logged h igh temperature m e t a , daz; d a t a logged ss w e l l as aqueous s o l u t e s . i n t o the syscem,nor do w e have comp-2tt: coverage of t h e Lor,ic salt type systems. Much of the mactine logging has t o awai: CL -:rm of che f i n a l retrieval format r a i n s u r e s h a t a l l :he necessary pazimetzz.r; were on hand foz in>or and cod,fyin&.
systems wizh gaseaus and Grgznic
The inethud to be used fo r :he c r i t i c a l evaluaz,or. ?T& .- most s tubborn problem bu t i t appear I tha: w e have reached whar: w. ;el i s a n e x c e l l e n t r e a a l u t i o n . For "iU2al" s ) a t r m s , t h e r e i s nc p r .I :m ccl che e v a l u a t i o n of t ne d a t a . The main l i ab lem c e n t e r s around -on- idea; and a s s o c i a t e d o r solvated type Sya-ems. We have j u s t 20ZlFLiLe6
work testing a new approach on some 30 non-ideal and associated systems and can report correlation an order of magnitude better than has hereto- fore been possible. This work is being written up at the present time and a manuscript will be available early this summer. feature of the developed method is that it will be possible to predict association or solvation even in the absence of diffusion data, on the basis of vapor-liquid equilibrium information, and thus also serve as a guide to the appropriate review procedure.
A particular
We have also begun to develop a format for contacting private industrial corporations on the possibility of contributing "in-house" data to the library. We feel this could be a significant contribution to the literature available for researchers in the field. While preliminary in- quires are out, I do not have any definite information to report in this regard. The early responses have been favorable, but no definite commit- ments have been received as yet.
DIFFUSICN COEFFICIENTS IN BINARY LIQUID SYSTEMS
UNIVERSITY OF MARYLAND
C C L L E G E PARK, MARYLAND
DEPT. OF CHEMICAL ENGINEERING
,
, CONTENTS
S E C T I O N 1 .o.oo. INTRODUCTORY TEXT
I
S E C T I O N 2 ...... TABLE 1 D I F F U S I O N C O E F F I C I E N T S I N B I N A R Y L I Q U I D SYSTEMS.
S E C T I O N 3 o o o o o o T A B L E 2 REFERENCE L I S T - N U M E R I C A L B Y YEARS
S E C T I O N 4 .o.ooo T A B L E 3 REFERENCE L I S T - A L P H A B E T I C A L 9 Y YEARS
S E C T I O N I
I N T R O D U C T O R Y T E X T
T H I S IS A C O M P I L A T I O N OF D A T A ON L I Q U I D P H A S E MOLCCULAA D I F F U S I O N C O E F F I C I E N T S AND I S THE R E S U L T O F A L I T E R A T U R E SURVEY. THE R E P O R T I N G OF T H E S t D A T A AND THE METHODS OF S T L K A G E AND K E J K I E V A L D E V E L O P E D ARE T H E I I V I T I A L S T A G E OF A PROGRAM D E S I G N E D FOR C O N T I N U I N G T A B U L A J I O N , E V A L U A T I U N , AND R E V I E W OF E X P E R I M E N T A L L Y D E T E R M I N E D L I Q U I D D I F F U S I O N
STAFiDAKD REFERENCE D A T A , A S A B A S I S FOR T E S T I N G E X I S T I N G THEORY, AND AS A G U I D E FOR THE OEVELOPMENT OF NEW D I F F U S I O N AND V I S C O S I T Y THEORY.
C U E F F I C I E N T S AILI: V I S C O S I T I E S . T H I S T A B U L A T I O N I S D E S I G N E D TO S E R V t AS
THE N O R K I S P A R T OF A PROGRAM SPONSORED BY THE N A T I O N A L A E R O N A U T I C S AND SPACE A D M I N I S T R A T I O N I N A S A CCtdTRACT NO- N G R - 2 0 - 0 0 2 - 0 5 3 -
B I N A R Y SYSTEMS I N C L U D E D ARE... ACUEOUS AND NONAQUEOUS S O L V E N J S W I T H I O N I Z I N G S O L U T E S P O L A R AND NONPOLAR O R G A N I C S O L V E N T S WIJH I O N I Z I N G OR
L I Q U I D SOLVEiVTS W I T H S L I G H T L Y S O L U B L E GAS S O L U T E S h O N i C N I ZING S O L U T E S
IN T H I S P R E L I M I N A R Y C O M P I L A T I O i i THE E X P E R I M E N T A L V A L U E S R E P O R T E D BY
T E M P E R A T U R E S H A V E B E E N CONVERTED TO C E N T I G R A D E D I F F U S I O I q C O E F F I C I E N T S H A V E B E E N CONVERTED T U T H E U N I T S 10-5 C M 2 / S E C C O N C E N T R A T I O N S H A V E BEElZl CONVEKTED TO S E L E C T E D U N I T S
T H E K E S E A R C t i E K ARE U N D I S T U R B E D , E X C E P T THAT- . .
S E L E C T I V E R E T R I E V A L
I N A U D I T I O N T O T H E E N T I R E T A B L E 9 S E L E C T I V E R E T R I E V A L C A N BE MADE OF
A S O L U T E OK A S O L V E N T A T E M P E R A T U R E L ) I F F U S I O i \ I C O E F F I C I E N T S A T I N F I N I T E D I L U T I O N ( L I M I T I N G V A L U E S ) A T Y P E C U E F F I C I E N T AN E X P E R I M E N T A L METHOD OF D E T E R M I N A T I O N OF D I F F U S I O N C O E F F I C I E N T A L I T E R A T U R E R E F E R E N C E R E F E R E N C E S 13y YEAR
ALL D A T A R E L A T E D T O .-.
S O L U J E AND S O L V E N T D E S I G N A T I O N
N G M F N C L A T U R E U S E D b Y T H E RESEARCHER IS F I R S T D E S I G N A T E D . WHEN THE COMPOUND NAME USE0 BY T H E AUTHOR I S D I F F E R E N T FRON NOMENCLATURE A D O P T E D FOR T A B U L A I I PURPOSES9 T H E SYNONYM IS G I V E N I N P A K E N T H E S I S .
D E S C R I P T I V E M A T E R I A L S 9 I N C L U D I N G S P E C I A L E X P E R I M E N T A L C O N D I T I O N S , ACCOMPANY THE S O L U T E Ah0 SOLVE;\IT D E S I G N A T I O N S FOR THE SYSTEM.
SOLUTE C O N C E N T R A T I O N
A L L C O N C E N T R A T I O N S A R E irZ; T E R E S QF S O L U T E U N L E S S NOTEO,.. -B = S U L V E N T CONCN. - X = A D D I T I V E ( O R OlHERi C6i.iCi'i. M = MOLAR MF = MOLE F R A C T I O N N = rVGRMAL WF = W E I G H T F R A C T I O N G / L = GKAMS P E R L I T E R G / G = GRAMS PER GRAM OF S U L V E N T
- 1
2 S I I
M/L = MULES P E H L I T E R M / G = MOLES PER GRAM OF S O L V E N T
D I F F U S I O N C O E F F I C I E N T - T Y P E AND METHOD
T H E T Y P E C O E F F I C I E N T REPORTED, AS D E S I G N A T E D B Y THE AUTHOR, AlUO THE PKOCEDU&ES UF E X P E R I M E N T A T I O N ' A h D A N A L Y S I S ARE CODED B Y A 6 - D I G I T f \ lUMBtR. C L A S S I F I C A T I O N S ARE MADE UN A GENERAL B A S I S AND NUMBERS ARE K E S E R V E D FOR A D D I T I O N A L A N 0 NONE D E T A I L E D C L A S S I F I C A T I O N . E A C H D I G I T I N THE CODE IS SEAKCHEO I N D I V I D U A L L Y .
T Y P E D I F F U S I O N C O E F F I C I E N T
COLUMN 1 COLUMN 2
1 M U T U A L 2 S E L F ( T K A C E R ) 3 TRACER I N TWO-COMPONENT
9 U N C L A S S I F I E D S Y S T E M
1 I N T t G K A L ( E X P E R I M E N T A L ) 2 D I F F E R E N T I A L 3 T I M E - A V E R A G E 4 E F F E C T I V E 9 U N C L A S S I F I E D ,
E X P E R I M E N T A L METHOD OF D E T E R M I N A T I O N ( C E L L C O N F I G U R A T I O N ) .
COLUMNS 3 AND 4
00 UPiREPGKTEO
10 F K E E D I F F U S I O N C E L L ( C O N C E N T R A T I O N G R A D I E N T I S FOLLOWED W I T H I N T H E C E L L )
20 R t S T K I C T E D D I F F U S I O N C E L L ( A ~ ~ L Y S I S IS M A O E OR c o N r m u m AFTER CONCENTRATION CHANGE H A S OCCURRED)
30 D I A P H R A G M C E L L , U N C L A S S I F I E O 31 D I A P H R A G M C E L L , V E R T I C A L ( S T O K E S - T Y P E ) ? S T I R R E D
3 3 D I A P H R A G M C E L L , NORThNUP-ANSON T Y P E * S T I R R E D 3 4 b I A P H d A G M C E L L , NOKTHRUP-ANSON T Y P E , NO STIRRING 35 C I A P H K A G M C E L L ? H D R I L O N T A L , S T I R R E D 3 6 D I A P H R A G M C E L L * H O R I Z O N T A L ? NO S T I R R I N G
32 I i I A P H R A G M C E L L , V E R T I C A L ( S T O K E S - T Y P E ) , NO S T I R R I N G
40 C A P I L L A R Y C E L L ? U N C L A S S I F I E D 41 C A P I L L A R Y C E L L , S T I R R E D 42 C A P I L L A R Y C E L L , NO S T I R R I N G
50 PCKOUS F R I T , U N C L A S S I F I E D
70 GAS A B S O ~ P T I O N METHOD? U N C L A S S I F I E D 71 C O L L A P S I N G B U B B L E 72 P K E S S U K E - T I M E D I F F U S I O N C E L L 7 3 A ~ S O R P T I O N I N T O LAKIFJAR J E T 74 ABSORPTION I N i u FAL~I:;G F!LM
9 1 NMR S P I N ECHO
99 U N C L A S S I F I E D
, I
METHOD O F A N A L Y S I S ( D E T E R M I N A T I O N OF C O N C E N T R A T I O N ) -
COLUMNS 5 A N D 6
I 00 UidREPORTED
10 I & T E R F E K L I R E T R I C , W I T H I N THE C E L L , U N C L A S S I F I E D 11 GUOY D I F F U S I O M E T E R 1 2 MACH-ZEIVDER D I F F U S I O M E T E K 1 3 P H I L P O r T O I F F U S I U M E T E K 14 K A Y L E I G H U I F F U S I O M E T E R
20 O P T I C A L , W I T H I N T H E C E L L , U N C L A S S I F I E O 2 1 C O L O R I M E T R I C 22 K I C R O S C G P I C 2 3 ? O L A R I M E T R I C 24 S P E C T R O S C O P I C 2 5 V I S U A L
3 0 GEFJERAL, W I T H I N T H E CELL , U N C L A S S I F I E D 3 1 C O N D U C T O M E T R I C 32 R A D I O M E T R I C ( T R A C E R C O U N T I N G )
40 O P T I C A L , O U T S I D E T H E CELL , U N C L A S S I F I E D 41 C O L O R I M E T R I C 42 P O L A R I M E T R I C 43 R E F R A C T I V E I N D E X D E T E R M I N A T I O N 44 S P E C T R O S C O P I C
5 0 GETJEAAL, O U T S I D E T H E CELL , U N C L A S S I F I E D 5 1 C H T O M A T O G R A P H I C 52 ZONDUCTUMETR I C 5 3 U E h S I T Y O E T E R M I N A T I U N 54 G R A V I M E T R I C
55 L j S M O T I C PRESSURE D E T E R M I N A T I O N 56 P O L A R O G R A P H I C 5 7 i t A D I O M E T R I C ( T R A C E R C O U N T I N G )
( I Y C L U O E S L O S S I N WEIGHT OF POROUS F R I T )
5 8 VOLUMETRIC
70 G A S A B S O R P T I O N R A T E MEASUREMENTS, U N C L A S S I F I E D
99 U N C L A S S I F I E D
E X P E R I M E N T A L P R E C I S I O N
A L L V A L U E S FOR E X P E R I M E N T A L P R E C I S I O N A R E + OR - PER C E N T U N L E S S O T H t K w i SE i\iGTEB.. .
AV = A B S O L U T E V A R I A N C E OF E X P E R I M E N i A i VALUES
R E F E R E A C E FOR D I F F U S I O N D A T A
E A C H R E F E R E N C E I S A S S I G N E D A U N I Q U E NUMaER. I N T A B L E S 2 A N D 3
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GAS DIFFUSION COEFFICIENTS
The previous six-month summary report indicated that a con-
siderable amount of gaseous diffusion data evaluation was still
required; the format for the presentation of results was uncertain,
and that a final report might be feasible by the end of 1967. A
final report was not completed because we received an extensive
report on an accurate investigation of noble gas diffusion coefficients.
Furthermore, we were able to extend the upper temperature range
of diffusivity for mixtures with polyatomic components using molecular
beam results. In addition, the lower temperature range of diffusion
coefficients was decreased for all gas pairs which had known London
constants. These two semi-theoretical applications of kinetic
theory have generated Standard Reference Data for approximately 40
gas pairs over for slightly more than two(%) decades of temperature.
It is now estimated that it will take the entire summer to write
the report on this evaluation of gaseous diffusion coefficients.
The format for the presentation of results will consist of
several means. The accuracy of gaseous diffusion data has been
classified according to percent uncertainty, as a function of tem-
perature, for each gas-pair. The most accurate Standard Reference
Data (SRD) is estimated to be 'rl% or better at room temperature,
22% at temperatures < 90°K, 25% at 1000°K, and 210% at 10,000'K.
Two other categories, over the same temperature range, have been
assigned for less accurate data.
u n c c X t n i n L i c s ax roci'il te::!pcrature.
good diffusion measurements available only over a very limited
teiuperaturo range.
These correspond to 52% and 2 3 %
A fourth SRD category is for
These four categories comprise the classification
- 2 -
of SRD for specific gas pairs. Unfortunately, this scheme does
not include a volummous amount of published results which are not
considered sufficiently accurate for Standard Reference Data. Such
poor measurements will be included in a separate annotated bibliography.
The evaluated SRD will be presented in simple equation form.
A mathematical equation was developed which would have a goodness
of fit consistent with the above accuracy categories.
obtained has the following general form.
The expression
The numerator alone fits the data of many gas pairs well; this as
a simple straight line on a log D12 vs. log T graph.
the denominator are necessary to modify D = ATS in systems which
have data over a wide temperature range.
The terms in
Data over a wide temper-
ature range elucidates molecular collision effects where the
attractive and upulsive forces are signigicant. The terme e c/T
e E/T2 account for attractive forces which are most important at
temperatures about room temperature or lower. This form is approxi-
mately equivlaent to the well-known Sutherland correction. The other,
denominator factor, [In (:)I2, is for repulsion forces effective
at very high temperatures, say temperatures greater than LOOOOK.
It is approximately the form for molecules with exponential re-
pulsion. The above general equation has been fitted to data for
approximately 40 gas pairs. In addition to this temperature relation
for SRD diffusion coefficients, another equation applicable at very
low temperatures, say in the order of 100°K, has also been developed
. t
-3-
for gas pairs which have known London constants.
D12 = a T 11’6 low temperature asymptote of gaseous diffusion co-
efficients assumes that only long-range attractive forces predominates
during intermolecular collisions.
It has the form
A third general mathematical expression has been developed which
acaounts for the composition dependence of the diffusion coefficient.
The expression is
where l + A (x)
{l+A (x=O. 5) D12(X) = D(x = 0 . 5 )
and x = mole fraction
x = mole fraction of heavy component
a,c = semi-theoretical constants for specific gas pairs. 1
The parameters, a and c, have been determined for about 70 gas pairs.
The value of CZ2 is based on the Lennard-Jones (12-6) potential and
is readily available from the literature.
In order to complement the presentation of results in equation
forms, graphs of the deviations of the data from the SRD equation
will also be prepared.
(CALCOMP) has been learned. Finally, for each gas-pair qualifying
remarks will be made such that the basis of data selection will be
well understood and amenable to any future additions by more accurate
measurements. The total format for the presentation of results as
here envisioned is consistant with the existing SRD publications of
other -physicak properties.
For this purpose, a digital plotting system
The evaluation and synthesis of accurate gaseous diffusion CO-
-4-
efficient data has confirmed the principle of corresponding states.
A set of accurate data for 10 noble gas pairs and H2-N2 was most
recently received by personal commnnication (Van Heynmgeir, R. J. J.,
thesis, University of Leiden (1967); published in Physica 3 8 , 1
(-1968)).
- These results along with diffusion coefficient values from
molecular beam data and known London constants have an extremely wide
temperature range. The results were considered relative to helium-
argon and by application of kinetic theory the data for all these
gas pairs reduced to one curve as a function of reduced temperature.
At very low temperatures, where classical behavior is effected by
quantum effects, the quantum deviations were evident in the diffusion
collision initegral.
quantum correction as a function of temperature and the deBoer para-
A method was also developed to estimate the
, meter. The synthesis of a corresponding states argument from the I
diffusion coefficient data is still preliminary; it is expected to
be completed only after the SRD report is prepared.
Diffusion in Polymer-Diluent Systems
The program to compile and evaluate diffusion coefficients in polymer-diluent systems has progressed asGanned. time data and references are being codified and placed on cards. We plan to use these cards to produce several types of data print out in tabular form and a l so to print bibliographies.
not had as much success as we had hoped in evaluating data because many systems have not been adequately described. can have a final report ready by the latter part of 1968.
At the present
Work continues on abstracting and evaluating data. We have
We feel that we
Diffusion in Inorganic Solids
The compilation of self-diffusion data in the alkali halides is continuing. The large active body of literature in this field is being plottqd and correlated with a least squares curve fitting computer program. This enables the data to be reduced to numerical form and to place confidence limits on the activation energy and pre-exponential terms in the equations. On the basis of these analysis coupled with critical review of the experimental work we hope to complete our selection of the best available equations for anion and cation self-diffusion coefficients within the next few months.
Turbulent Transport Coefficients
We have accumulated and cataloged copies of nearly all pub- lications containing turbulent transport data published during the past ten years. Work is now underway on abstracting and evaluating the data. This process of compilation and evaluation is now the major activity of this portion of the program.
Personnel
The investigation of diffusion in gases is directed by Dr. E. A .
Mason. He is assisted by one graduate student, Mr. T. R. Marrero.
-L-
The liquid piffusion survey is directed by Dr. R. B. Beckmann with the assistance of two graduate students, Mr. D. K. Harris and Mr. P. N. Vashist, and a part-time research associate, Mrs. M. C. Bailey.
T h e investigation of diffusion in inorganic solids is directed by Dr. L. P. Skolnick. He is assisted by one graduate student, Mr.
I G. Slawecki.
T h e polymer diffusion survey is directed by Dr. T. G. Smith, with the assistance of a graduate student, Mr. Ronald Heck.
Dr. J. M. Marchello is directing the turbulent transport sur- vey and is assisted by one graduate student, Mr. E. F. Logan.