Technical Mote 195— THE EFFECT OF TEMPERATURE ON THE DENSITY AND ELECTRICAL RESISTIVITY OF SODIUM CHLORIDE SOLUTIONS J. d. ARPS, THE BRITISH-AMERICAN OIL PRODUCING CO., DALLAS, TEXAS, MEMBER AIME ABSTRACT This paper is a study of the effect of temperature on the electrical resistivity ‘of sodium chloride solutions besed on the published resistivity and density data in the International Critical Tables. This temperature effect considerable importance in quant interpretation of electric logs, where it is frequently necessary to correct mud ivities measured under surface 38 to temperatures existing at the bottom of the bore hole. An empiri- cal approximation formula was de- veloped for this conversion which has proved to be very useful and seems to provide results well within the range of accuracy of the data involved. This approximation formula stat a Diener reas J= (Reds, SE, were sistivities of sodium chloride solutions at temperatures of f and t, degrees Fahrenheit, respectively INTRODUCTION Research by various investigators during the past 20 years has clarified the physical principles of the phe- nomena which cause the natural or spontaneous electric potential in rotary drilled bore holes. The basic relation: ship which is most commonly used reads: Rae R, in which the SP deflection, as measured from the shale base line, is expressed in nillivolts, K is a constant, which ap- pears to vary between 50 and 110; the low value applying to shaly sends, whereas the higher values are more common in carbonate rocks. A good average value for K= 70, for which value there is considerable theoretical justification.” SPay = —K logy a In order to calculate the resistivity of the connate water R- and to estimate its “equivalent salinity” (as NaCl) from an electric log by means of this SP relationship from a knowledge of the static self potential and of the resistiv. Vol. 198, 1953 ity of the mud filtrate Rus, it is neces sary to first correct the resistivity of the mud filtrate measured under sur- face conditions to the resistivity of this same mud filtrate in the well hore at a different temperature. In order to make this temperature conversion for the mud filtrate the va- tiation of the electrical resistivity of sodium chloride solutions with tem- perature is commonly used. Since some discrepancies were found in the charts ordinarily used for this purpose, it was felt desirable to make # new study of this relationship based on the published ‘measurement data, Because of the {un- damental nature of these relationships fand as an aid to other workers in this field, an attempt has been made in this study to show every step in the cal culations, CONDUCTIVITY VS MOL CONCENTRATION ‘The most complete published refer. cence on the temperature relationship of tium chloride solutions of different concentrations is provided in the Inter- national Critical Tables’ The basic ‘measurement data on the electrical con- ductivity of aqueous sodium chloride solutions, at different temperatures, as ssiven in these tables, are reproduced in Table 1. ‘The electrical conductivity values ‘Ain this Table 1 are expressed as 10" times the specific conductivity & in ohm*em per unit of concentration in milligram mols per liter of solution Cor: 2. @) ole A= 108 RESISTIVITY VS MOL CONCENTRATION ‘These conductivity values from Table 1 were first converted to the correspond- ing electrical resistivity values (Ry) expressed in ohm-meters, as is conven- Table 1" — Electrical Conductivity \ of Aqueous Sodium Chloride Solu- tions as a Funetion of Concentration C: and Temperature t. (Expressed as 10° times the specific conductivity in ohm“cm” per unit of con centration in milligram mols per liter of solution) eae 107.88 107.60 106951380, e192? 682 1058112803 642 «10854 12088 632 1072118. 6? 940585 5959551 M108, 5a7 109.01 siz ons 856 = ass 10135 58 a076 98.31 99 as 749 ns 6866 365 ek 315 6 265 aa 246 spate from Rel 2. ‘TEMPERATURE IN DEGREES FAHRENHEIT + mera? sis wi sé wig 8525, 1936 88a sti wor BHD. 15 335048 sit m9 54 - oa 3087 irl 82 sii sits iis 253 ALS, 1536 87) mis 74a : 2686 : 218 aires istiee whore ‘Probably erroneot, should be for 212° F, PETROLEUM TRANSACTIONS, AIME 307——————__-_ tional in electric logging practice. Since ‘Table 2 — Specific Gravity g. or Density (g/cc) of Aqueous Sodium Chlo- 5 ride Solutions as a Funetion of Sodium Chloride Weight Percentages (Re). by definition equals ay and and Temperatures t. ee since, according to Equation 2, k Peat ‘TEMPERATURE IN DEGREES FAHRENHEIT « 30"A Cu the conversion can be made weineehe % i a fromthe data of Table 1 with the ‘Loo7s? 1.00559 o.gat82 09651 relationship: 101509 012s Ltoiel 0.9719 10! 03038102728 TOSs1 0.9855 Raa + Yo4s75 oats Tn2919 0.9904 eK To6t2i 105653 1ois26 1.0134 Ce ime Lone teres one ie results of this conversion are Too2s4 — Tnp6i2 Tian 1.0820 presented in Table 4, which shows Tioaz¢ 110166 Yie7s 1.0565 this resistivity (Ry), a8 @ function of concentration C, and temperature ¢. It also shows the corresponding ppm (parts per million) values which, how- ever, were arrived at in a different manner, as will be discussed hereafter. rio10 Loris. Tes. 1086 Tis8 11017 vags2 1172 Veils 11381 Tipo 1.1492 Tigost 113381 i566 14874 116105 Ties Lives 1 2 4 6 3 0 2 4 6 Lizai9 Loe B a 2 Fr Ed “Interpolated between 44° and eu? “toats01 x SPECIFIC GRAVITY VS ee MOL CONCENTRATION ‘Table 3—Concentration C, of Aqueous Sodium Chloride Solutions in Mil- We now have relationship. which ligram Mole per Liter of Solution as a Function of Sodium Chloride provides the electrical resistivity of @ Concentration by Weight (ppm) and Temperature ¢, folution of given weight of sodium chloride in a given volume of solution. ‘TEMPERATURE IN DEGREES FAHRENHEIT ¢ This volume of solution, however, de- pends in turn on the concentration of sodium chloride by weight and on the temperature, and itis therefore neces sary first to establish the relationship between concentration in parts per mil lion and specific gravity for various temperatures. The required data for this conversion were also cbisined from the International Critical Tables? They are reproduced in Table 2, which shows: ‘eciic gravity g, or density in grams yer cubic centimeter at various tem- peratures t for different concentrations txpressed as weight percent NaCl. The seu saa se ase Tage) 172059 «17178 «170200 «Mes NS sos 37336 346510 BasTe ga 728 josiss —T0S014 701660 69425 LOTSA 1,069,460 1067199 1.056.482 Ya52.469 114460050 1.449.765 1.477.901 Teiz207 Ypa2989 LR2a553 11300290 2BwAle 2230460 2224773 200.8% 265465 2638711 2631.60% 25602969 Sorrsss 3057875 SolaTl 3015.775 Botte 3daasse Sa7adsl 3.430585, 3957-673 31930676 3'919.008 3.874.690 ‘ais732 4384725 $371.93 4.301.400 ‘fpe6.182 $1951.051 53860934 5.820.264 ‘Table 4— Electrical Resistivity (Re). of Aqueous Sodium Chloride Solutions in Ohm-meters for Various Tem- peratures £ as a Function of Sodium Chloride Concentration C, or as Parts per Million by Weight. Citar ase 1 T eit = or war ar ae me at | " — we [ee |e [| oe | te m= [te a “te = | fs = | Hs = | Ba whee | = Becaay, | acamlors | simon : aerleg | i eB | Sl scan | BERS | meio | scoops i Behe | ae fees | Balsa | BRB | se fo | ara oem i Bei | ube BG/SE, | RVR BE ) gea VERE | wh joins | toe [a : abraded eae | ee Eee | BE) ERS | ate [tiem] etn jim ‘ Hee | ary eae a8 | ERD | ES | GBR) Bie | oct : ae) Ee ce | he | CE | lay ors rae 8 #7 | £Bh| ate 5" | gaat] tat | tune] sae lois Bae od & ey | Sia) a | GESTED | SSS ume) = E = | le = ff ee 8 ee | Uae EE |) = |= (BB ERY = IE | = YE § Lees SJE] = (= IBS ie be La = |= 23 LH i ie | ewe = fa EB aS jawed = [= PS [S" 1 Condon dta were reported in LOT. or BP Fabel be 17 328 PETROLEUM TRANSACTIONS, AIME Vol. 198, 1953Table 5—Electrical Resistivity (Re), in Ohmvmeters and Ratio (Rv)x/(Re)s of Aqueous Sodium Chloride Solutions for Various Temperatures t as a Function of Sodium Chloride Concentration ‘Siam Corde per Million by Weight. TEMPERATURE IN DEGREES FAHRENHEIT Ga'pom by weg) = wae 7 rca ae 7 o (Re), 147.0105 91.1872 781909 50,1520 28.6560 214719 (Rye/ (Re) 1 16125 1.88015 2.93130 5.13018 684665 100 We, eia074 5.0804 47-2224 302861 173268 12.9807 eR. 1.61232 188062 2.93228, S254 684150 300 We), 0.1407 18.7255 16.0682 10.3099 5.9028 4645 pe). OF, 160861 1.87697 2.92347 Sols .ras62 1,000 We), 5.81792 4908 3.24205 184581 139497 (Rada/ (Re Lo7es 187131 2.88530 5.06786 6.70574 3,000 We), 2.03200 175034 114824 65155 "99395 (a/R, 10158 185925 asa 00g 6'38836 6,000 i} LostiT 911432 ‘60004 34124 25784 mR e/tR) 158734 T8416 279063 91762 6550826 10,000 1656130 56682 31273 : 157539 1.89522 7782 93622 30,000 23729 20588 136328 07243 1555498, 1.79565 2270649 5.09n6 100,000 ‘082789 02577 ~ 155588, ones 200,000 e 01549 S s.1se8 Ave 159078 1.88013 2.8438 5.05398 66iss0 ——7Sibwo values for 644°F were obtained by linear interpolation between the 50°F and 68°F values of the tables. The values for 284°F and 312.8°F above the boiling point of water were not available in the critical tables for salt solutions and were therefore estimated by respectively multiplying the specific sgravities of salt solutions at 68°F with the ratio of 0.92084 between the specific gravity of water at 284°F and at 68°F and the ratio of 0.91301 for temper- atures of 312.8°F and 68°F" From these data Table 3 was prepared, which shows. concentration Cy in milligram mols per liter of solution at temperature {as a function of weight concentration in ppm obtained from the relationship: ex ppm =f ) RESISTIVITY VS WEIGHT CONCENTRATION In order to obtain the desired rela tionship between resistivity (Ry) and ‘weight concentration in ppm it was nec- essary to interpolate between the values of Table 3 to obtain the weight con- centration (ppm) for the Cx values and temperatures of Tables 1 and 4. Combination of this interpolated (ppm) date with the resistivity (Ry), data for the same C, and t values yielded a direct relationship between (Re), and ppm for various temperatures t, as shown in Table 4, and depicted on the double logarithmic chart of Fig. 1. For a series of weight concentrations of 60, 100, 300, 1,000, 3,000, 6,000, 110,000, 30,000, 100,000, and 200,000 ppm the corresponding electrical. re- Vol. 198, 1953 sistvities (Ry), at temperatures. of 32°, 644°, 77°, 212°, 284° and 312.8° were then computed by direct inter- polation between the data of Table 4 and Fig. 1 under the assumption that fover limited intervals the relationship between (Re), and ppm for a given temperature is a straight line on double log paper. That this assumption is a reasonable one to make may be mote from a close inspection of Fig. 1. This interpolation led to the data in Table 5. In addition to the calculated resistiv- ities, we have also shown in this table the ratio (Re)n/(Re)« of the resistiv ity of @ salt solution of given con- z 3 a SEE. ee S0UM cALORDE CONCENTRATION AS PARTS PER LLIN Y MEIONT RESISTIVITY OnMS PER SOUARE METER PER wETER FIG. 1 — ELECTRICAL RESISTIVITY OF SODIUM CHLORIDE SOLUTIONS VS CONCENTRATION IN PPM AND TEMPERATURE. PETROLEUM TRANSACTIONS, AIME 3290 T| Rance fei te ret his ae erature | Average eto fer aie terperetarg r | rot — 1 t | Fy) | rit wut a ' oh 30 + a egos i {i a a | rly [lobe czesoere ve. 707) | | 40 sl 4 4 1 1 v 1 | {it 1 { 1 \ so 1 ili H rit ' |i 4 1 } L 1 fifi iit 1 t i tla i | | Ltt dah de th def 1 30 100 130, 7200 280 "300 ‘t+ TEMPERATURE IN DEGREES FANRENHEIT FIG. 2 — LINEAR RELATIONSHIP BETWEEN TEMPERATURE AND THE RATIO. OF RESISTIVITY (Bey oF 32° F AND RESISTIVITY (Re), AT # centration at 32°F to the resistivity of this same solution at a higher tem- perature. It will be noted that these ratios are reasonably constant for a fiven temperature throughout. the en- tire salinity range studied. ‘The aver- age ratios (corrected for the missing high salinity figures by the trends in. (Re) and (Ry)om are shown at the bottom of this table. ‘These ratios were then plotted as ordinates on the chart of Fig. 2 against the temperature in degrees Fahrenheit as abcissa; the averages are shown as circles, From inspection ofthe chart of Fig. 2 it will be observed that the ratios (Re)n/(Re) very nearly seem 10 fol- low a linear’ pattern with respect to temperature, The equation of such a ‘straight line relationship, as determined by the “method of least squares” and as shown on Fig. 2, is: (Ren 4 GEIE= 000906 6 +67). . 8) As a first approximation for the tem- perature correction factor this relation- ship will be quite satisfactory, although {for subsurface temperatures below 150° 330 ("FOR SODIUM CHLORIDE SOLUTIONS. F the calculated ratios will be slightly above the true values. In order to con: vert the electrical resistivity of a salt solution which is measured under sur- face conditions at a temperature °F to the resistivity of the same salt solution ata bore hole temperature of 1," this simplified or first approximation relationship reduces t 14627 (Re) = Re) 8 6TT & (Ro) ht? fab, o For quick resistivity correction this is a simple and handy formula. Its use- fulness may be illustrated with the fol: lowing example Resistivity mud filtrate measured at the surface at a temperature of 64.4°F is 656 ohm-meters (R,) What is the resistivity of this same mud filtrate under bottom hole conditions at 122°F. With Equation 6: 4d +7 (Ree = 6562 FFF = 363 ohm-meters. From inspection of Table 5, from which this example was taken, it may PETROLEUM TRANSACTIONS, AIME Tbe noted that the true resistivity at 122"F (10,000 ppm) is 373 ohm- meters. NOMENCLATURE SP = static self potential in nillvolts K = constant in SP relationship (ranges from 50 to 110 with 70 as a good average value) Raq = electrical resistivity of mud filtrate in obm-meters R, = electrical resistivity of in. terstitial or connate water in ohm-meters| logy = logarithm to the base 10 A= electrical conductivity, ex- pressed as 10° times the specific conductivity in cohm’em" per unit of concentration in milli- gram mols per liter of solution ‘= specific conductivity in ‘ohmem'* , = concentration in milligram mols per liter of solution at a temperature ¢ temperature in degrees Fahrenheit (Ry) = electrical resistivity of salt solution at temper in ohm-meters electrical resist hit in ohrm-meters| = specific gravity or density in grams per cubic cen- timeter ppm = parts per million sodium chloride by weight 58.45 = molecular weight of NaCl REFERENCES Mounce, W. D., and Rust, W. M., “Natural Potentials. in Well Log: ging,” Trans. AIME (Geophysics), (1945) 164, 288, 2 Doll, H. G., “The SP. Log: Theo- retical Analysis and Principles of Interpretation,” Trans. AIME, (1949) 179, 146. 3. Wallie, MR. J., “A Quantitative Analysis of “the Electrochemical Component of the SP Curve,” Trans. AIME (1949) 186, 17. 4, International Critical Tables of Nu- merical Data, Physics, Chem. and Techn., (1929) IV, 283. 5. International Critical Tables of Nu- merical Data, Physics, Chem. and Techn, (1928) II, 79. 6. Handbook of Chemistry and Physics, 82nd ed., 1,789. eee Vol. 198, 1953