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TJNCLASSIFIED

This document consists 02


pages. copy
01"
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Series A .

Contract No.

W-7405, eng.

26

Reactor Experimental Engineering


Division
J

S &ND HEAT CAPACITIES OF STAINLESS

STEEL (316), ZIRCONIUM, AM) LITHIUM AT EmVATED TEMPEXA!JXRES

R. F. Redmond
J. iknes

OAK RIDGE NATIONAL

LABORATORY

operated by
CARBIDE AND CARBON CHEMICALS C O M F ' ~
Union Carbide and Carbon Corporation
Post Office Box P
Oak Ridge, Tennessee

UNcLASsrFm

3 4 4 5 b 0353335 5
..

--

~RJIIJ 1342
Physics

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86*
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.tq

EXTERNAL D ISTRIBUT1OM

me

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TABU OF CONTEmTs

IXTRODUCTION

HEAT CAPACITY OF S m m S S STEEL

IEAT CAPACITY OF ZlRCOhTIU&I

HEAT CAPACI!TT OF LI!PEIUM

LIST OF FIGURES

1. Schematic drawing of calorimeter


2. Graph of s t a i n l e s s s t e e l enthalpy with temperature
3 - Graph of zirconium enthalpy with temperature
4 0 Graph of lithium enthalpy with temperature
5 . Graph of zirconium and lithium heat capacities with
teaperatwe
LIST OF TABLES

1. Enthalpy 2. Enthalpy 3 . Conrparison


4, Enthalpy 5 . Comparison

temperature data for s t a i n l e s s s t e e l


temperature data f o r zirconium
of zirconium data
temperature data f o r lithium
of lithium data

18
20
21
22
24

UNCLASSIFIED

SUMMARY

The purpose of t h i s investigation was the determination of the heat cap a c i t i e s of zirconium and lithium a t elevated temperatures,

I n making these

measurements, secondary information on the heat capacity of s t a i n l e s s s t e e l and


the r e l a t i v e enthalpies of the t h e e materials a t elevated temperatures were also
obtained.

The zirconium data extend the temperature range for which zirconium

heat capacities have been reported,

The lithium data have been obtained i n m

e f f o r t t o appraise the widely d i f f e r i n g r e s u l t s previously reported by other


investigators e
A bunsen i c e calorimeter was used t o determine the r e l a t i v e enthalpies of

t h e materials as a function of temperature,

The heat capacities were obtained by

d i f f e r e n t i a t i n g the experimentally determined enthalpy temperature equations

The heat capacities obtained i n t h i s manner were as follows:


Zirconium

Cp = 0,070

3.6

T(cal/g OC),

where 15OoC 4 T% k105O0C


Lithium
Cp = 1.00

where 2OO0C

2.8 x

= O.,lOg

where

150%

OC),

L TC C llOO*C

Stainless S t e e l (type

cP

lom5T(cal/g

'

316)

5.,7 x lom5T(c&/g

6 TOC L~OOO'C

OC),

The estimated e r r o r of these valu-es is t

55,

and is based on determinations

made with a synthetic sapphire calorimetric standard.


LNllRODUCTION

The apparatus and procedure used t o determine the r e l a t i v e enthalpies of


t h e various materials as a function of t e q e r a t u r e has been described i n a
preTrious report (1)
I n b r i e f , t h e r e l a t i v e ' enthalpy ( r e l a t i v e t o OC)

of t h e material was

measured a t a number of temperatures by means of an i c e calorimeter (shown


schematically i n Figure 11, To do t h i s , t h e capsuled sample was heated i n a
furnace t o a constant temperature, and was then dropped i n t o t h e calorimeter
where t h e t o t a l enthalpy of t h e capsule and its contents, r e f e r r e d t o OC
(temperature of calorimeter), vas measured.

To obtain t h e enthalpy of t h e

sample alone t h e enthalpy of t h e empty capsule vas subtracted.

The enthalpy

of t h e empty capsule was determined i n t h e same manner as the enthalpy of t h e


f i l l e d capsule.
The enthalpy data f o r each material were correlated by t h e least-squares
method, using an equation of the form

%-

Eo = a

+ bT +

C T * ~ When d i f f e r -

entiated, the enthalpy equation yielded the heat capacity equation i n t h e

form Cp = b

2cTo

Reat capacity values for synthetic sapphire, previously determined (1)


,
agreed within

576 of t h e values reported by the TTational Bureau of Standards.

On t h e b a s i s of this agreedent, t h e heat capacity values presented i n t'his


report are estimated t o be accurate v i t h i n

'*

spec if ied,

t 5% over

t h e temperature ranges

'

HEAT CAPACITY OF STAINLESS STEEL ("'E33 316)


A s s t a i n l e s s s t e e l was used as t h e capsule m t e r i a l t o contain t h e

zirconium and l i t h i m samples, the enthalpy-temperature r e l a t i o n foi' this


material had t o be determined.
The stainless s t e e l capsules were machined from stock of' t h e r^ollowing
spectrographically determined composition:
Composition

Standard Error

oi'

10

0.12

10

1.49

0.026

0.004

Si

0.55

Cr

17.0

12.2

0.5

Ni
Mo

'

2*3

4 t o t a l 02 51 enthalpy measurements vas made.

0.5

1
The r e s u l t s axe shown i n

Table 1 and are compared with t h e valiies f o r t h e enthalpy obtained from the

c o r r e l a t i n g equation,

mcI;AssIFm

'7

The least-squares equation f o r the d a t a i s


q(S)

q(S) =

where 150C

1.54 +-

TC

0.109 T

+ 2.83 x 10-5 T2 (-)c a l

t 1)

1000C

The data and the equation values a r e shown graphically i n Figure 2.


Because of the form used here f o r the enthalpy equation, t h e heat capacity equation for s t a i n l e s s s t e e l derived from it is l i n e a r .

The heat

capacity equation, obtained by d i f f e r e n t i a t i n g t h e enthalpy equation, i s


Cp (cal/gC) = 0.109

+ 5.66 x 10-5 T (+ 5%)

where 2OO0C L TC .d 1000C

HEAT CAPACITY OF ZIRCONIUM

Samples of zirconium m e t a l vere obtained within ORNL.

ZrF2 by C a O andCaI2 furnished a melt of zirconium.

Reduction 03

From t h e c a s t metal

several plugs weye machined t o f i t stainless s t e e l capsules.

The plugs were

X-ray examined f o r inclusions and were found Lo be honogeneous.

The z i r c o n i q

plugs were sealed i n t o capsules by a heliarc weld around the capsule cover.

UNCMSSIFIA)

The spectrographically determined analysis of the zirconium metal a f t e r

.>

machining w a s :
PPm

A1

I'In

200

Ba

4 400

hb

Be

.L. 0.1

Ni

200

Ca

40

Pb

20

ca

400

Hf

co

4 10

Si

100

Cr

20

Sn

h 20

CU

200

Ti

40

Fe

10,000

Mg

400

10,000

L 20

Zn

6 10

For a given enthalpy determination the procedure was:


1. The t o t a l heat content of t h e capsule f i l l e d with zirconium
was measured.
2.

The heat content f o r the capsule material was subtracted.

3.

The r e s u l t i n g zirconium heat content vas reduced t o a u n i t


weight basis.

The enthalpy-temperature r e l a t i o n obtained using t h e l e a s t -squares method is


%(S)

Q(S)

where 150C L TC

0.107
L

0.070 T

1050C

+ 1.8 x

T2(F)

(3)

UMCLASSIFIED

The data a r e shown i n Table 2 and the observed values a r e compzed with
t h e equation'values f o r t h e same temperatures.
The derived heat capacity equation is
Cp ( c a l / g

+ 3.6

= 0.070

OC)

x 10-5 T

(4)

where 15OoC L T o & h 1000C

K. K. Kelley ( 6 ) , using t h e results of Jaeger-Veenstra, gives t h e


equation
Cp ( c a l / g

%)

0.0467

4.54 x

614
+T2

where 298% L TK h 900K


Several enthalpy and heat capacity comparisons a r e given i n Table 3 .

HEAT CAPACITY OF LITHIUM


O i l f r e e lithium, obtained from t h e Metalloy Company, was scraped clean

under an atmosphere of argon; t h e lithium w a s then placed i n stainless s t e e l


capsules which were sealed by h e l i a r c welding.
The analysis of t h e l i t h i u m furnished by t h e manufacturer is given below:

Ca

O.O@

Al

- O.Ol'$

Fe

- O.OOl$

Ha

0.002

0.005%

oeo6$o
nil

When t h e lithium was squeezed under a hydraulic press, a l a y e r of o i l -

w a s produced on t h e press p l a t e , indicating that t h e lithium bars s t i l l contained

some o i l .

10

UNCLASSIFDD

After t h e measurements were made, two capsules were opened and t h e lithium
samples were analyzed.

This d a l y s i s indicated t h e amount of impurities pro-

duced by corrosion and exposure t o a i r .

This analysis i s shown below:


Sample AJ

Sample AH
Wi

50-54 ppm

Ni

1170-1215 ppm

Fe

885-920 ppm

Fe

2'j"j'O-Fj'OO ppm

Cr

1ppm

(2

500 P P

0.074%

0.048$

A t o t a l of
*

.,

lithium.

69 enthalpy measurements vas made w i t h seven samples of

I n contrast t o t h e s t a i n l e s s s t e e l and zirconium enthalpy values,

t h e lithium values exhibited considerably more scattering.

To simplify computation, t h e arithmetic average of t h e experimental values


i n small i n t e r v a l s w a s calculated.

an equation f o r t h e data.

The average values were used t o determine

The d a t a and the average values a r e shown i n Table

The equation obtained for t h e enthalpy data was:

- H,(S)

= 89.9

1.00 T

+ 1*4x

10-5 T2

cal
(7)

where 250C 4 TC h. l l 0 O o C
The curve of t h i s equation is p l o t t e d i n Figure 4 with the averaged data

values indicated.
The derived heat capacity equation f o r l i q u i d lithium is
Cp (cal/g

OC)

= 1.00

2,8 x 10-5 T

where 250C h TC h U O O C

(t 574)

4.

Several investigators have studied lithium, and the various heat capacity' values reported i n t h e l i t e r a t u r e are compared i n Figure 5 .
comparisons are shown Z n Table 5.
I

/tks

.'

Tabulated

. .

UNcLASsLFm

12

*.

IZGEREXCES

1. Redmond, R., b n e s , J., "The Design, and Construction of an


Ice Calorimeter" - ORNL-1040

-\

'.

2.

Bates, A., Smith, Do, "Specific Heat and Enthalpy of Liquid


Lithium i n the Range of 500C - 1000C." M.I.T. Practice
School Report K-729, O a k Ridge, (1951)

3.

Landolt -Bornstein, "Physikalisch-Chemische Tabellen, 'I


Supplementary Volume 3, Part 3 , J u l i u s Springer, Berlin, 1936

4.

Cabbage, A, M., "Enthalpy, Mean Heat Capacity, and Absolute Heat


Capacity of Solid and Liquid Lithium," NEPA 1370-SCR-58,
MEPA, O a k Ridge (1950)

5.

Yaggee, F. L., and Untermyer, S., ''The Relative Thermal


Conductivities of Liquid Lithium, Sodium, and Eutectic NaK,
and t h e Specific Heat of Liquid Lithium, ML-4458, Argonne
National Laboratory, Chicago, (1950)

6. Jaeger, F.

M.; Veenstra, W. A , , The Exact Measurement of the


Specific Heats of Solid Substances a t Higher Temperatures. V I 1
The Calorimetrical Behavior of Zirconium. Rec. t r a v . Chim.,
vol. 53, 1934, p o 917. Kelley, K O K., Contributions t o t h e Data
on Theoretical Metallurgy X, Bureau of Mines Bulletin 476

UNCLASSIFIED
DWG. 11590
*\

.
THERMOCOUPLE1

m - F U S E

CIRCUIT
BURETTES 8r
CAPILLARY,

ARGON---------//
R

ICE BATH

LUCITE SHEL

ICE MANTLE
AROUND FINS

.
Fig. I.

Schematic Drawing of Apparatus

W I D 3 oH-*H

AdlWHlN3

I-

Y)

W
W

cn
cn

cn

c9

cu

t-

-W
.-c

cn

3j

W
Q

(D

II

In

I-

r
I

I
0
y.

cn
>
W

Q
0

fc
w

ci,

ii

.
8

E ) / l D 3 OH -% A d l V H l N 3

.N

I-

E)/ 1033

OH-lH

AdltlHlN3

I-

In

*
+

I-

9
-

o
(
u
o

ri

I
*o0

16

r
c

UNCLASSIFIED
DWG. 16395

SEE K. K . KELLY ( 7 )

0.060

r)

V1

A
A
.

0.

1.40

LITHIUM:

1.20

---

NEPA

1-Z-A

LANDOLT-BORNSTEIN

1.

0
0

200

400

600
TEMPERATURE,

800
OC

1000

I,

tI-

1200

17

18

mcLASsIFm

TABLE 1
TABULATED ENTfTALPY DATA FOR

316 STAINLESS STEEL


Difference
ObS. - Calce
CdIg

Temperature
I

OC

137
146
152
176

15 099
17 32
18 97
21 95
24.28
28 75
31.40
35 009
36 60
36 95
9

202

, J

236
255
284
298
301
344
354
355
396
404
404
408
410
417
420
466
._ 467
477
480

528

43 70
42 90
50.60
51.20
51.00
50 60
50.80
52.20
54,60
59 080
56.20
60.60
60.10
47 -70

531
534
551
594
597
598

68.50
70.40
76.68
78 61
76 d 97

-0 02
0

-0.05
-0.59
-0 07
e

-1.01
+l.
34

-0.88

+o .17
+o .29
-0.49
-0 16
+o 15
+o .23

41 90
*

-1e 05

17.Oh
18 10
18 80
21.66
24077
28 91
31* 25
34 86
36 62
37 -00
42.49
43 77
43 91
49.26
50.31
50.31
50.84
51.10
52.04
52.43
58.61
58 75
60 12
60.51
67 3.5
67.46
67 98
70.36
76 -45
76.86
77 003

+o .89
+o .69
-0.24
-0.30

+o 16
+2 17
e

4-1.19
-2.55
+O 38
-0 41

69.00

+0.55

+l.
54

' .

+0.52

+O .04
+O .23
+I* 75

-0.06

(Continued)

UESCLASSIFIED

UNCLASSIFIED

:-,

TABU 1 (Continued)
Difference
Calc.

Obs.

Temperature
oc

602
617
637
663
666
688
690
696
740
762
788
806
807
871.
876
896
919
949
987
1003

1013

-P.

cau13
77-70
78.20
83 * 35
87 -72
88,22

09-70
87 30
91 02
96 13
99-56
107 6
106 2
106.8 .
118.2
115.5
122 6
125 .o
129.0
137 2
143 5
0

143.0

77 90
79.76
82.65
86,46
86.90
90 13
90 -43
91.31
97 93
101 27
0

105.2
108.0
108 2
118.2

u9.0
122.2

125.8
13007
137 0
139 6
141.3
0

-0 * 20

-1.56
+o .70
+1.26
+l.
32
-0 e43

-3 13
-0 29

-1.80
-1.71
+2.4
-1.8
-1.4
0

-3.5
+0,4
-0.8
. -1.7
+0.2

+3*9
+1.7

20

TABLE 2

TAl3ULA!IED ENTRALgy DATA FOR ZIRCOKCUM

-HOW

Tenrperature

C&/g
C a l c u l a t ea

OC

Equation 3

'f

131
139
186
195
236
246
308
314
350
365
370
424
497
500
538
544
622
641
680
726
796
834
841
906
912
972
1014
1036

10 30
0

io. 15

12~69
13 63
16 19
17 938
25 .oo
22.90
27 14
28.15
28.36
31 62
39 * 87
40-35
43 32
42,30
50 50
50 52
55 J.3.
60.94
67.66
72 26
69 89
78013
75 e76
84057
89 079
92.44
0

9.35
9.93
13.48
14 17
17 35
18 13
23.08
23056
26.50
r7 074
28 16
32.66
39 00
59.26
42 62
43 17
50-24
52.01
55 065
60.03
66.85
70 62
71 31
77 090
78 52
84-74
89 18
91.52
0

Difference
Obs.

- Calc.

+0-95

+o

22

-0.79
-0 044
-1-16
-0 075
+1.92
-0.66
+O 64
+0.41

+o

20

-1004
+o 87
+1 09
+o -70
-0.87
+o 26
-1-49
-0.54
+o 91
1-0.81
+1 64
-1.42
+o .23
-2.76
-0.17
+o .61
+o 92
e

21

UNCLASSIFIED

TABLE

COM?ARISON OF SOME QRNL HEAT CAPACITY AND


EEl3AWY VALUES FQR ZIRCONIUM W I T H DATA
OF JAFGER-vEENSTRA
TC

Jaeger Veenstra (6)


%-Eo ( c a v g 1

ORNL

%-Eo ( c 4 3 )

Jaeger
Veenstra (6)
Cp(cal/g OC)

ORNL

Cp(cal/g

200

13 -74

14.5

0.0710

0.077

400

28 e 67

30.7

0.0786

0.084

600

45 *23

48.2

0.0870

0.091

OC)

22

UNcLPssIFm
TABU 4

TABULATED ENTHALPY DATA FOR LITHIVS


LJ'

TC

' ,i

230
274
307
310
370
403
406
418
474
479
527
541
561
577
608
612
617
619
648
664
686
687
696
710
728
729

332 1
343.0
0

520 0
482 0

Mean

qa>-Ho(S)

Difference

Temperature OC

Equation 5

Hean

ca113

c d g
- Eq- 5

230.0
274 *O
308 5

332.5

320.8
365 -2
400.0

+11.3

343 -0
416.9

370

462.4

462.2

0.2

409

499 9

501.6

1.7

493

565 09

586 .I

-20-9

559-7

666.3

654 5

+ ~ . 8

614

702~8

709.7

- 6.9

681-8

784 -7

778 8

5.4

740

838.6

838.2

0.4

-22.2

+16,9

553.0
652.0
662.9
683.1
694.0
692 0
684.0
741 0
774 1
790 -0
781.2
780 0
769 3
810 -7
839 00
814 -0
e

730

797 -0

734
736
737
744
746
746
748
748

817 .o
805 .o
838.0
856.0
862.0
848 0
890 .o

UNCLASSIFIED

23
TABU 4 (Continued)

.-!

Difference
cal/g
Mean - E. 5

i\

756
762
766
766
792
803
807
816
847
854
866
,871
884
895
910
936
941
942
949
960
965
990
1000

1006
1012
1018

826.9
887 -4
923 0
909 2
929 * 2
968.0
945 -4
909 0
966 .I?.
972-1
984.8
1028..
1063.
1050.

762.5

871.2

861.2

+10.0

804.5

917 -6

904.1

+13 5

869* 5

957.6

970 -7

-13-1

1052

1046

+6

1018

1098

1123

-25

1088

1210

la95

+15

943 3

1082.
1012.

1095
1062.
1060.
1135
1020

1024
1029

1034
1036
1037
1065
1098

llo1

1058.
1153.
996
1215
1217.
1199.

rl
0

0
+I

rl
+I

=I

n
rl

a3

+I

rl

Ln

9
-lJ

cu

\D

rl

ch

+'

0
I

+I

9
rl

+I

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