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Excess Volume and Viscosity of Ethoxy Ethanol with N-Butylamine, Sec

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Excess Volume and Viscosity of Ethoxy Ethanol with N-Butylamine, Sec In dian Journ al of Chemi stry Vo l. 43A, September 2004, P ). 1876-1 88 1 Excess volume and vi scosity of ethoxy of amines and alkoxy alcohols make the m intcresting ethanol with n-butylamine, sec-butylamine, fo r our study. A survey of the literature has show n tert-butylamine, n-hexylamine, n-octylamine th at no attempts have been made to study excess volumes and viscosity of binary mi xtures of eth oxy and cyclohexylamine eth anol (EEL) with a seri es of amin es whi ch include Il-butylamine (NBA ), sec-butylamine (SB A) , Me S Subha*, G Na rayana Swa my, M Eswari Bai & terl-butylamine (TBA), n-hexy lam ine (N HA), K S V Kri shn a Rao Il-octylamine (N OA) and cy cl ohexylamin e (CH A) at Department of Chemistry, Sri Kri shn adevaraya Uni versity, 308.15 K aiming for a wider understanding of th e An<1nt apur 5 I 5 003, Ind ia molecular interac ti ons involved. Email : mcssubha@rediffmail .com Recei ved 6 Jal/uC/I }' 2003; revised 28 JUI/ e 2004 Experimental Density measurements were made using bi capill ary Densiti es and viscosities of eth ox y eth anol (E EL) with 1/ ­ pyc nometer hav in g a capillary di ameter of 0.85 mm. butylam ine (N BA), sec-butylamine (SB A), lert-but ylami ne The pycnometer was calibrated using do ubl y di still ed (TBA ), I/ -hexylamin e (N HA), I/ -octylam in e (NOA) and water and th e necessary bu oyancy correc ti ons were cyclohexy lami ne (C HA) have been measured at 308.15 K. From the ex peri me ntal data the excess vo lu me (0'), deviati on in appli ed. The density values were reproducibl e within 3 viscosity ( llE) and the excess molar Gibb's free energy of the ± 0.2 Kgm· . A th ermostaticall y contro ll ed water bath activati on of viscous fl ow (C*E) have been comput ed and capabl e of maintai nin g the temperature constant to l presented as functi on of composition. The parameter d of th e ± 0.02 K was used for th e studies. Grunberg and Nissan has been calcul ated. The observed vari ati ons Vi scosity measurements were made usin g of th e properti es for the above mi xtures conclude th at the in teracti ons betwecn - unlike molecul es predominate over the Ubbelh ocle viscometer. The time of efflu x of a dissociati on effects in th e individual components. It is al so evident constant vo lume of liquid through the capill ary was that th e presence of strong interac ti ons between unli ke molecu les measured with th e help of a pre-calibrated ROCA R is predomin ant and characteri zed by the negati ve vE and positi ve stop watch capabl e of recording ± 0.1 s. The llE, C *E and d l values. The excess volume, deviation in viscosit y and excess molar Gibb's free energy of the ac tivati on of viscous viscometer was ke pt verti cal in a th ermos tat at 308.1 5 fl ow hav e been fitt ed to Red li ch-Ki ster equ ati on to deri ve the K and th e efflu x time for water at 308. 15 K was fo und coe ffi cient s and standard dev iati ons. to be about 302 s. The fl ow time of pure liquids and IPC Code: lilt C17. GOIN 9/04; GOI N 11 /02 li quid mixtures was measured a number of times and the average of the readi ngs was taken. In chemi cal industry there exi sts a continuing need fo r The vi scosity was calculated fro m the average of reli abl e thermodynami c data of binary systems. effl ux time and density p accord ing to: A survey of the literature shows th at very few attempts t·3 have been made to study excess properti es TJ/p = at-bit ... (1) for mixtures containing alkoxy alcohols. Amines and 4 5 alkoxy alcohols . in th eir pure state exhibit self­ where a and b are the characteri sti c constants of the associati on through hydrogen bonding. Amincs are viscometer. These were determined by taking water, better electron donors , which all ow them to have benzene, carbontetrachloride and acetonitrile as specific interac tions. Further, amin es fo rm water calibratin g liquids. The kinetic energy correc ti ons in so luble compounds of medicin al importance. The were calculated from these values and they were molecular interaction study of alkoxy alcohols is of found to be negli gible. The viscosity measurements interest because of investi gating the effect of were accurate to ± 0.5x I 0-4 kg m·t s·t . simultaneous presence of ether and alcoholi c Ethoxy eth anol and all the amines we re purchased function al groups in the same mol ec ule. The presence from Merck KGOA , Germ any. Th e chemi cal s were of etheri al oxygen enhances the ability of the -OH di stilled and kept ti ghtly sealed and protected fro m group of the same molecule to form hydrogen bonds atmos pheric moisture and carbondi oxide as fa r as 6 7 with other organi c mol ecules . These characteri stics poss ible. Prior to measurements, all liq uid s were kept NOTES ]877 over 0.4 nm molecular sieves to reduce water content In each case, the optimum number of coefficients, Aj , and were partially degassed under vacuum. The was determined from an examination of th e variati on purities of these chemicals were checked by of standard devi at ion, cr( yE) as calculated by measuring their densities and comparin g with those s 9 reported in literature . Mi xtures were prepared by mixing weighed amounts of the pure liquids adopting ... (8) the method of closed system. The measurements were made with proper care in an AC room to avoid where m is the number of ex perimental data and II is evaporati on losses. the number of coeffici ents in Eq. 8. Aj coefficients considered (n = 5 in the present case), have been Results and discussion presented in Table 2. The excess functions 1{ and 0, Grunberg and From Table ], it is observed that the vi scosity of lo Nissan interaction parameter i and the Gibb's free binary liquid mixtures under study varied non-linearly energy of activ ati on of viscous flow C*E were with the mol e fraction of EEL (XEEL) . This suggests calculated respecti vely from Eqs 2 to 5. the presence of intermolecul ar interacti ons between unlike mol ec ul es of these mixtures. A simil ar s 11 E = 11 - [x 11 1 + (I-x) 11 2] ... (2) observation was made by Narayana Swamy et al. from the viscosity studies of binary liquid mixtures of 0 = V - [XVI + ( l-x)V ] . (3) 2 acetonitrile + amines. From Fig. ], it is observed that is negati ve over In 11= x ln 111 + (1-x) In 11 2 + x(1-x)i ... (4) 0 the whole range of composi tion and increases in the order of increase with size of the normal amine molecule. But in the case of EEL + NBA, + SBA and The molar vo lume V of a mi xture is calculated usi ng + TBA positi ve 0 va lues are observed only at hi gher Eq.6. mole fractions of EEL. An interpretati on to th is behaviour can be given using the experience made V=M/p .. (6) with the quantitative evalu ation of alcohol + amin e mixtures by the ERAS model proposed by the earl ier where M = xM I + (I-X)M2' X is a mole fraction of workers 12- 16. The observed negative excess vo lu mes component 1, MI and M2 are molecul ar weights of may be explained in terms of two opposing effects. compounds I and 2 respectively. Mixing of EEL with different amines will induce the The measured density (p) and viscosity (11) at mutual dissociati on of component mol ecul es and the 308.15 K for the mixtures of 2-ethoxyethanol (EEL) + fo rmation of hydrogen bonds between unli ke II-butylamine (NBA), + sec-butylamine (SBA), + terl­ molecules. The former effect leads to positive excess butylamine (TBA), + II-h exylamine (NHA), + /l­ volume and the latter effect leads to negative excess octy lamine (NOA) and + cyclohexylamine (CHA) are vo lume. The actual volume change wou ld depend used to calculate the excess molar volume (0), upon the rel ative strength s of the two effects. The E dev iati on in viscosity ( 11 ), excess Gibb's free energy observed negative va lues of 0 show th at the main of activati on of viscous fl ow (C*E) and Grunberg­ contribution to 0 is due to hydrogen bond formati on l Nissan interaction parameter (d ) and the results are (OH ...... N) between unlike molecules. Moreover, the presented in Table I. negative values of VI:: may also be partly due to the The va ri ation of the parameters 0 and 11 E with the specific acid-base interactions between EEL and mole fraction of EEL (XEEL) for the systems under amine molecules by considering EEL as Lew is acid study are graphically shown in Fi gs 1 and 2 and amines as Lewis bases.
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