Conseguences of soil crude oil pollution on some wood properties of olive trees Chemistry |141 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Study the Density of the Double Salt (Ammonium iron (II) sulfate) Dissolved in Water and Ethylene Glycol at Different Temperatures Nagham H. Abood Dept. of Applied Science Chemistry/University of Technology Received in:8/January/2017,Accepted in:22/February/2017 Abstract Densities of double salt [(NH4)2Fe(SO4)2.6H2O] dissolved in distilled water and in ethylene glycol at three temperatures (298.15,303.15 and 308.15)k have been utilized to calculate the apparent molar volume , limiting apparent molar volume ,experimental slop . These results provide as information about solute-solvent, solute-solute interaction and structure-forming, structure-breaking tendency from partial molar expansibility . Key words: double salt, partial molar volume, solute –solvent, solute-solute interactions. Chemistry |142 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Introduction Ammonium iron (II)sulfate or Mohr’s salt, is the inorganic compound with the formula [(NH4)2Fe (SO4)2.6H2O] containing two different cations, Fe +2 and NH4 +1 It is classified as a double salt and ammonium sulfate. It is a common laboratory reagent like the other ferrous sulfate salts , ferrous ammonium sulfate dissolves in water to give the aqueous complex [ Fe(H2O)6] +2 , which has octahedral molecular geometry[1].This compound is a member of a group of double sulfates called Schöintes or Tutton’s salt , which form monoclinic crystals and have formula M2N(SO4)2.6H2O [2]from its application in analytical chemistry,this salt is preferredover other salts of ferrous sulfate for titration purposes as it is much less prone to oxidation by air to iron(III).The oxidation of solutions of iron (II) is very pH dependent occurring much more readily at high PH. The ammonium ions make solutions of Mohr’s salt slightly acidic, which is slow this oxidation process[3]also there is new application of this salt which has been found in an organic reaction in which the knoevenagel condensation, Michael addition and intermolecular cyclization of 4-hydroxoumarin,malononitrile and aromatic aldehydes led to novel and known pyranocoumarins. Simple operation, the use of readily accessible commercial starting materials, good to excellent yields and short reaction times show efficiency of this method for the synthesis of these biologically interesting products[4].This model compounds in waterand ethylene glycol as solvents helps to understand some thermodynamic properties of solutions[5] ion-water interactions which are very important in chemistry, ions effect on the rates of chemical reaction [6]. Ion –exchange mechanisms used for chemical separations [7] and in this study we will discuss the solute –solute, solute-solvent interactions in the solution of (salt+water) and (salt+ ethylene glycol) at different temperatures as well as the structure- making/breaking tendency of the solute (salt)in the given solutions. Experimental section Material The double salt [(NH4)2Fe (SO4)2.6H2O] was provided by BDH chemical (England), ethylene glycol (EG), (HOCH2CH2OH) was provided by Sd Fine-chem-limited (SDFCL). A series of concentration from complex salt was prepared in range (0.025-0.3)M at different temperatures, the molal concentration were calculated from molar concentration (C) mol/L using eq (1) [8] Where in g/mol is the molecular weight of double salt. Densities measurements Densities of solutions were measured by using pycnometer(25)ml which were calibrated with doubly distilled water at three temperatures (298.15,303.15 and 308.15)k the densities of solution were calculated by weights using balance Sartorius BL 2105(Germany) with an accuracy of 10 -4 gm after reaching thermal equilibrium with a water bath at the studied temperature, divided by the volume of pycnometer. Chemistry |143 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Results and discussion The practical data of densities of solution (salt +H2O) and (salt + EG) at (298.15, 303.15 and 308.15) k. were listed in table (1)and the relationship between the density and the molalconcentration were shown in figures (1) and (2). Table (1) exhibits that the density values of solution in both solvents water and ethylene glycol increased with increasing concentration, in addition these values decrease with increasing temperature at the same concentration. These results agree with general behavior of liquid solutions. Values of density of solution are plotted versus molar concentration then treated with linear model by the least square approximation by the following equation Where are coefficientThe correlation coefficient (R 2 )and standard deviation (σ) are listed in table (2) which are an evident that a good agreement with a linear model.The standard deviation (σ) was estimated from equation (3) [∑ ] Where ρexp,ρcalarethe experimental and calculated density respectively, P is the number of the coefficient in equation (2), N is number of experimental points. To understand the nature of solute –solvent and solute –solute interactions of this solution we calculated the apparent molar volume ( ) (cm 3 /mole) from equation (4)[9] ( ) Where ρ,ρ° are the densities of solution and solvent respectively.(m) is the molal concentration of complex salt in (mole/kg). The values of apparent molar volume of the investigated solute are listed in table (3) and shown in figures (3) and (4). These figures clearly show that the values of do not respond in a linear manner at the whole concentration range of the job for both solvents, this case can be attributed to the higher order attractions among solute particles. For this reason the interest was focused on the low concentration region (below 0.1 molal) where these higher order interactions can be neglected, in addition to estimate the partial molar volume at infinite dilution or limiting apparent molar volume (cm 3 .mol -1 ) which considered as a measure of solute –solvent interactions and a measure of molecular volume of solute [10] by using the masons Empirical equation (5)[11] √ Where the experimental slope which is a measure of solute-solute interactions[12]. The calculated values of and ,from the intercept and slope the plottes the values of versus the root concentration √ are listed in table (4),the plots are shown in figures (5) and (6). In table (4) we can see the values of were large negative inwater and have an oscillating character with varying temperature which indicates a weak solute –solvent interaction, at the Chemistry |144 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 same time the values of in water are large positive reflecting a strong solute-solute interaction nature which explain the reason behind the non-linear behavior of at concentrations above 0.1 molal, this strong attraction is understood in the light of tendency of Fe +2 ions to precipitate as Fe(OH)2 in neutral aqueous solution (Ksp=8×10 -16 ) which means the minimum pH to prevent precipitation of iron(ii) ion is 5[12]. In the EG solvent, the values are negative too but at 298.15 k is less negative than in water then the value becomes more and more negative with increasing temperature, this may be due to the formation of some kind of complex between EG molecules and iron ion, but with increasing temperature the stability of this complex decreased as this is clear from the decrease of solute-solvent interaction with increasing temperature. On the other hand the solute –solute interaction increases with increasing temperature reflecting the fact of reducing the capability of dissolution of the salt in EG at higher temperatures. The relationship between the limited partial molar volume and temperature are according by the following equation (6) The values of first derivative which called partial molar expansibility [13] (QE) have been calculated and listed in the table (5)which is a measure to structure –forming, structure – breaking affinity to solute molecules on lengthy range order of solvent molecules,in table (5) the values of (QE) are negative in both solvents and this indicate the salt perform as structure breaking behavior, this effect is more strong in EG solvent than on water because the hydrogen bonding network in EG is weaker than that in water so it can be concluded that the salt causes a long range damage to the solvent structure in EG than that it does to the water. References 1- Green, W.;Norman, N.; Alan, S.;Earn,(1997). Chemistry of the elements (2nded),Butter worth-heiemann. Wiley-Interscience ISBN 0-08-037941-9. 2- Housecroft, C.E.;and Sharpe, A.G. (2008). Inorganic Chemistry(5thed), NewYork.Wily- Interscience,ISBN 0-471-84997-9 . 3-Staab V.K. (2013).Ammonium Ferrous Sulphate 100 g (Mohr's Salt)International Journal of Science and Research (IJSR),4(9). 4-Karami,B.;khodabakhsi,S. andEskandari, Kh.( 2016).New application of Mohr's Salt J.Bentham Science, 13,(10),105-110. 5- Yilmaz,H., (2002). Excess properties of alcohol-water system at 298.15 k Turk.J.Phys.26:243-246. 6- Krop,X.and Bakker F. ,(2001).Dynamics of water molecule in Aqueous solvation hells .Science 291:2118-2120 Chemistry |145 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 7- Habuchi S.; KimH.B.and Kitamura N.(2001). How Ion affect the Structure of water Anal.chem.73:366-372 8- Thakur,R.C.;Sharma,R.and Sanjay,K.,(2015).Thermodynamic Study of calcium chloride and magnesium chloride in Binary aqueous mixtures of Sucrose at differentTemperatures.J.Chemical and pharmaceutical Research,7(1),176-181. 9- Koyeli,D.;Mahendra,N.R.,(2016).Study on Solution behavior of some oxalate salts in aqueous vitamin solutions Indian.Journal of Advances in Chemical Science,138-148. 10- Thakur,R.C.; Sonika(2014).Effect of Temperature on partial molar volumes of some bivalent transition metal chlorides and magnesium chloride in the water-rich region of binary aqueous mixtures of ethanol. J. Pharma, Bio and Chem. Sci.5(6),1298-1305. 11-Masson,D.O. (1929). Solute molecular Volume in relation to Solvation and Ionization philosophical Magazine 8,218-235. 12-Christian, G. (2016).Analytical Chemistry,6 th edition(Wiley). 13- Chourey, V.R. and Sikarwar, S.K. (2016) .Apparent molar volume, Density and Viscometric Studies of Alcohol in Aqueous Solution at Different Temperatures. International Journal of Science and Research (IJSR)5,(9). Chemistry |146 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Table (1) Values of practical densities ρ (gm.cm -3 ) of (salt + water)and(salt +EG) at (298.15, 303.15 and 308.15) k. C (mole/L) (g.cm -3 ) in H2O 298 k 303 k 308 k Solvent (H2O) 0.99704 0.99565 0.99403 0.025 1.03546 1.03463 1.03275 0.030 1.03654 1.03567 1.03422 0.035 1.03790 1.03661 1.03487 0.040 1.03795 1.03773 1.03613 0.045 1.04054 1.03888 1.03792 0.050 1.04235 1.04100 1.03982 0.100 1.05366 1.05190 1.05053 0.150 1.06528 1.06021 1.06139 0.200 1.07623 1.07423 1.07357 0.250 1.08857 1.08592 1.08583 C (mole/L) (g.cm -3 ) in EG 298 k 303 k 308 k Solvent (EG) 1.1061 1.1042 1.1026 0.025 1.14313 1.14549 1.14486 0.030 1.14618 1.14710 1.14632 0.035 1.14778 1.14829 1.14710 0.040 1.14798 1.14880 1.14671 0.045 1.14901 1.14960 1.14804 0.05 1.15342 1.15208 1.15038 0.100 1.16272 1.16275 1.15962 0.150 1.17073 1.17059 1.16692 0.200 1.17036 1.18144 1.17203 0.250 1.17405 1.1820 1.18965 0.300 1.19085 1.19303 1.19111 Table (2) Values of empirical parameters a (gm.cm -3 ) b (gm.cm -3 .mol -1 .L), R 2 correlation and standard deviation for (salt + water) and (salt +EG). Density parameters in H2O T/k a(gm.cm -3 ) b(gm.cm -3 .mol -1 .L) R 2 σ 298 1.0301 0.2285 0.998 0.00461 303 1.029 0.2226 0.998 0.00532 308 1.0274 0.2296 0.999 0.00632 Density parameters in EG T/k a(gm.cm -3 ) b(gm.cm -3 .mol -1 .L) R 2 σ 298 1.143 0.152 0.947 0.00557 303 1.1425 0.1777 0.989 0.00444 308 1.1408 0.175 0.983 0.00699 Chemistry |147 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Table (3a): The values of apparent molar volume of (salt +H2O) at (298.15, 303.15 and308.15) k. Root concentration (cm 3 .mole -1 ) in H2O 298 k 298 k 298 k 0.158 -1147.90 -1172.24 -1163.53 0.173 -927.14 -945.91 -953.35 0.187 -777.48 -781.60 -779.31 0.200 -632.43 -662.79 -664.38 0.212 -576.32 -571.01 -586.61 0.224 -515.63 -517.19 -526.89 0.316 -174.58 -171.14 -173.88 0.387 -62.95 -38.44 -57.28 0.447 -3.81 -0.75 -5.58 0.500 26.09 31.18 25.08 0.548 60.00 60.76 55.01 Table (3b): The values of apparent molar volume of (salt + EG) at (298.15,303.15 and308.15) k Root concentration (cm 3 .mole -1 ) in EG 298 k 298 k 298 k 0.158 -980.96 -1140.54 -1177.31 0.173 -850.35 -939.92 -965.95 0.187 -719.45 -785.76 -797.47 0.200 -589.82 -654.56 -644.44 0.212 -505.55 -558.47 -560.25 0.224 -499.17 -512.03 -511.03 0.316 -156.48 -175.13 -161.45 0.387 -34.39 -45.71 -33.25 0.447 52.31 5.38 40.81 0.500 109.16 58.10 39.84 0.548 99.41 86.97 88.06 Table (4): Limiting apparent molar volume ( ), experimental slop for(salt +H2O) and (salt + EG) at different temperatures. (salt+H2O) T/K 298 -2614.9 9628.4 303 -2694.0 9975.5 308 -2647.0 9711.1 (salt+ EG) T/K 298 -2205.4 7873.3 303 -2638.7 9739.6 308 -2771.2 10372.0 Chemistry |148 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Table (5): Apparent molal expansibility for the salt in both solvents System QE Salt + H2O -3.21 Salt +EG -56.58 Figure (1): Density data of [(NH4)2Fe (SO4)2.6H2O] in H2O Figure (2): Density data of [(NH4)2Fe (SO4)2.6H2O] in EG 1.02000 1.03000 1.04000 1.05000 1.06000 1.07000 1.08000 1.09000 1.10000 1.11000 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 ρ ( g /c m ^ 3 ) m (mole/kg) 298 K 303 K 308 K 1.14000 1.15000 1.16000 1.17000 1.18000 1.19000 1.20000 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 ρ ( g /c m ^ 3 ) m (mole/kg) 298 K 303 K 308 K Chemistry |149 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Figure (3): Apparent molal volume of [(NH4)2Fe (SO4)2.6H2O] in H2O Figure (4) :Apparent molal volume of [(NH4)2Fe (SO4)2.6H2O] in EG -1400.00 -1200.00 -1000.00 -800.00 -600.00 -400.00 -200.00 0.00 200.00 0.000 0.100 0.200 0.300 0.400 0.500 0.600 Q v ( cm ^ 3 /m o le ) molal^0.5 298 K 303 K Series3 -1400.00 -1200.00 -1000.00 -800.00 -600.00 -400.00 -200.00 0.00 200.00 0.000 0.100 0.200 0.300 0.400 0.500 0.600 Q v root concentration 298 K 303 K 308 K Chemistry |150 2017(عام 2العدد ) 30هجلة إبن الهيثن للعلىم الصرفة والتطبيقية الوجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (2) 2017 Figure (5): Linearized initial segment of vs square root of the molal concentration of [(NH4)2Fe (SO4)2.6H2O] in H2O Figure (6): Linearized initial segment of vs square root of the molal concentration of [(NH4)2Fe (SO4)2.6H2O] in EG. y = 9628.4x - 2614.9 R² = 0.9622 -1500.00 -1000.00 -500.00 0.00 0.0 0.1 0.2 0.3 Q v ( cm ^ 3 /m o le ) root m 298.15 k y = 9975.5x - 2694 R² = 0.9679 -1500.00 -1000.00 -500.00 0.00 0.0 0.1 0.2 0.3 Q v ( cm ^ 3 /m o le ) root m 303.15 k y = 9711.1x - 2647 R² = 0.9668 -1500.00 -1000.00 -500.00 0.00 0.0 0.1 0.2 0.3 Q v ( cm ^ 3 /m o le ) root m 308.15 k y = 9739.6x - 2638.7 R² = 0.976 -1500.00 -1000.00 -500.00 0.00 0.0 0.1 0.2 0.3 Q v ( cm ^ 3 /m o le ) root m 303.15 k y = 10372x - 2771.2 R² = 0.9709 -1500.00 -1000.00 -500.00 0.00 0.0 0.1 0.2 0.3 Q v ( cm ^ 3 /m o le ) root m 308.15 k