Chemical and Process Engineering Research ISSN 2224-7467 (Paper) ISSN 2225-0913 (Online) Vol.

6, 2013

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Boiling Point Determination Using Formular Method

Atume Emmanuel Terhemen (Corresponding author) Faculty of Natural sciences, University of Jos PMB 2084, Jos Plateau State, Nigeria Tel: +234 8073532478, E-mail: atumeemmanuel@gmail.com Abstract The boiling points of n-alkanes were determined using formular method and compared with experimental results, this method depends on three major factors which includes; the molar mass of a compound, the energy that the compound posses and the energy that the compound absorbs from its surrounding, the formular gave 99% accuracy. This method is highly favored at very low entropy. It can be applicable in the petroleum industry, agrochemical industry, reactor design process and proof for the existence of a conventional inductive effect in relatively neutral molecules. Key words: Boiling point determination, Atumes formular, Inductive pressure, internal molecular energy, External energy, Atumes hypothesis 1. Introduction The properties of highly disordered systems are best explained by the kinetic theory of gases (Ababio et al. 2001). Which includes; Boyles law, Charles law, Avogadros law and the general gas equation for ideal gases. At high pressure, gaseous molecules (C1-C4 n-alkanes) liquefy and become more orderly so they tend to deviate from these laws due to changes in their properties and a change of state from gas to liquid. (Ababio et al. 2001). Consequently, the limitations of the gas laws gave rise to the emergence of a liquid and solid hypothesis which is known as the Atumes hypothesis. Boiling point determination of n-alkanes using the Atumes formular can make up a very useful standard for the kinetic theory of liquids and solids. Considering the n-alkane series; C1-C4 are gases at room temperature so they obey the gas laws. C5 (liquid) posses both liquid and gaseous properties so it has wider deviation from the liquid hypothesis, C6-C17 are liquids while C18 and above are solids. (Arun 2009) Finally, liquids and solids obey the Atumes hypothesis while gases do not. 2. Atumes formular for liquid n-alkanes is given as: M2 B Where M N ln (2N-4) B = = = Molar mass of n-alkane in gmol-1 Number of carbon atoms in a molecule of n-alkane =
2

[(N-5) 0.2 +3.027] 2 ln (2N-4)

Natural logarithm of the Internal molecular energy = External energy in g2 mol-2 K-1 (Jeffrey & Gibbings 2012)

[(N-5) 0.2+3.027]

Boiling point in Kelvin

Chemical and Process Engineering Research ISSN 2224-7467 (Paper) ISSN 2225-0913 (Online) Vol.6, 2013

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2.1 Worked Example Calculate the boiling point of n-hexane in degree Celsius given that the Atumes series for liquid n-alkanes is equal to [(N-5) 0.2 +3.027]2 g2 mol-2 K-1 Solution Molar mass of n-hexane = CnH2n+2 = [(12x6) + (2x6)+2] = 86gmol-1 B = 862 [(6-5)0.2+3.027]2 ln[(2x6)-4] B = 7396 (3.227)2 ln(8) B = 341.5K T0C = TK - 273K T0C = 341.5 - 273 T0C = 68.50C Table 1.Comparism between experimental and calculated results of the boiling Points n-alkanes S/N Compound Formular Boiling point (0C) Experimental result (Arun 2009) 68.7 98.4 125.7 150.8 174.1 270.6 Boiling point (0C) Calculated result 68.5 96.8 124.6 150.9 175.4 272.8 Deviation (0C) - 0.2 - 1.6 - 1.1 + 0.1 + 1.3 + 2.2 % Deviation 0.3 1.6 0.8 0.2 0.7 0.8 % Accuracy 99.7 98.4 99.2 99.8 99.3 99.2

1. 2. 3. 4. 5. 6.

n-hexane n-heptane n-octane n-nonane n-decane n-pentadecane

CH3(CH2)4CH3 CH3(CH2)5CH3 CH3(CH2)6CH3 CH3(CH2)7CH3 CH3(CH2)8CH3 CH3(CH2)13CH3

From table 1 above, B => B M

2

---- Equation (1)

Chemical and Process Engineering Research ISSN 2224-7467 (Paper) ISSN 2225-0913 (Online) Vol.6, 2013

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Atumes hypothesis states that the boiling point in Kelvin of an n-alkane if liquid or solid is directly proportional to the square of its molar mass and inversely proportional to the natural logarithm of its internal molecular energy and the square of its external energy. 3. ASSUMPTIONS 1. A conventional inductive effect exist within the molecule of an n-alkane such that the carbon atoms at the extremes pumps electrons into the central carbon atom(s) E.g. CC-C-CC

Left extreme

Central carbon atoms

Right extreme

2. The molecule experiences an immediate elastic repulsion of electrons from the central carbon atom(s) back to the extreme carbon atom(s) by a force known as Inductive Pressure (p). 3. The pumping in and out of electrons is extremely very fast, resulting into kinetic energy from within the molecule and this energy is not high enough to cause dissociation into ions or breakage of the bonds within the molecule. 4. As the size of the molecule increases, the conventional inductive effect also increase with increasing number of carbon atoms, but after the second carbon atom, the effect dies down completely so that a maximum of 2 carbon atoms pumps electrons into the central carbon chain from both extremes making a total of 4 carbon atoms. That is the effective repulsion of electrons is proportional to 2(N-2) units which is equal to k (2N-4) units. This implies that B (2N-4) units. 5. Nevertheless, as the length of the central carbon chain increase, the inductive pressure decreases due the increase in the total cross sectional area or volume. Therefore, the inductive pressure is inversely proportional to (2N-4) units i.e. p p = 1 (2N-4) (k) 1 (2N-4) units If the value of K is unity then, p = 1 (2N-4) units 3.1 Proof: Let us start by integrating p because the central carbon atoms operate as a collective unit and not as individual atoms. p = 1 (2N-4) units 1 (2N-4) dp => B 1 --- Equation (2) P

p dp =

p = ln (2N-4) units = natural logarithm of the internal molecular energy It is expected that p alone will not be sufficient to cause boiling to take place for liquids and solids so it will absorb sufficient energy from a source of heat which is proportional to the inverse of [(N-5) 0.2 +3.027]2 units for liquids. The figures below were estimated from experimental results for the external kinetic energy of some liquid n-alkanes.

Chemical and Process Engineering Research ISSN 2224-7467 (Paper) ISSN 2225-0913 (Online) Vol.6, 2013

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Table 2. External kinetic energies of some n-alkanes (Atume, 2012) Compound n-pentane n-hexane n-heptane n-octane n-nonane n-decane 4. Observations from Table 2 1. The first digit in all cases for liquids is constant but it is equal to 3 for the first five cases and it changes after every five consecutive n-alkanes provided that there is no change of state. 2. The first decimal set of values forms an arithmetic progression with A.P. = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, , n and a common difference of 0.2 3. The second decimal set of values is random but statistically, 0.02 seem to appear most frequently so we consider 0.02 as the next decimal value to the A.P. 4. Other digits are very uncertain so we round them up to 0.007. Therefore: For n-pentane = 3 + 0.0 + 0.02 + 0.007 = 3.027 For n-hexane =3 + 0.2 + 0.02 + 0.007 = 3.227 For n-heptane = 3 + 0.4 + 0.02 + 0.007 = 3.427 For n-octane = 3 + 0.6 + 0.02 + 0.007 = 3.627 and so on. Generally, we have [(N-5) 0.2 + 3.027] units as a representation of the external kinetic energy for all liquid state nalkanes and this is known as the Atumes series for liquid state n-alkanes. Similarly, the external kinetic energy for solids is equivalent to [(N-5) 0.2 + 5.027] units. The total energy of a molecule at any instance during boiling is a factor of the natural logarithm of its internal molecular energy and the external kinetic energy and it is always constant and unique for each molecule. The electrons within the molecule are very sensitive to temperature so as the external energy (temperature) increases, the electrons become more and more energetic thereby increasing the rate of pumping in and out of electrons to and fro within the molecule, this molecule will continue to absorb energy until it can no longer hold it again, at this point the thermometer reading becomes constant then we say boiling is said to have taken place. Hence, an increase in the external kinetic energy will cause a corresponding increase in the internal energy and this implies that boiling point is also inversely proportional to both the internal and external energy that is external energy multiplied by p is equal to a constant [(N-5) 0.2 + 3.027]2 x p = constant The external kinetic energy is always approximately five times the natural logarithm of the internal molecular energy => Boiling Point is also inversely proportional to External kinetic energy in g2 mol-2 K-1 3.0595 3.2266 3.4196 3.6218 3.8274 4.0330

Chemical and Process Engineering Research ISSN 2224-7467 (Paper) ISSN 2225-0913 (Online) Vol.6, 2013
[(N-5) 0.2 + 3.027]2 ---- Equation (3)

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It is very important to note that the deviation in degree Celsius ( 0C) of the formular results from the experimental results in table 1 above is caused by the uncertainties in the second and third decimal set of values of the external kinetic energy values in table 2.

We cannot rule out the possibility of having the deviation coming from the experimental results instead of the calculated results. Practically, the deviation could be as a result of indeterminate error (random error) due to variation in external conditions, which cannot be controlled. Included here would be errors due to barometric pressure, slight variation of temperature and movement of air current (Joan & Siddharth 2009) Hence: B => B B M M2 1 P 1 B [(N-5) 0.2 + 3.027] M2 B = [(N-5) 0.2 + 3.027]2 ln (2N-4)
2

---- Equation (1) ---- Equation (2) ---- Equation (3)

Combining Equations (1), (2) and (3)

Also, for solids, M2 B = [(N-5) 0.2 + 5.027]2 ln (2N-4) This is the Atumes formular Finally, C1 C4 obeys gas laws because they are gases, and their internal molecular energy alone is high enough to cause boiling to take place even without heating. However C5 is the closest liquid to gases so it posses both liquid and gaseous properties with the widest range of deviation of the calculated result from the experimental result: experimental result is equal to 36.10C; calculated result is equal to 42.80C with a deviation of +6.70C. It will be very logical to attribute the volatility of petrol or petroleum ether to this high deviation because; 1. Petroleum ether is made up of C4-C7 alkanes with higher percentage of C5 alkanes. 2. Petroleum ether is liquid yet it behaves like gases with very low flash point. 5. Applications: Petroleum Industry: Atumes formular can be used to estimate the gross and net quantity of heat and energy that each liquid fraction of n-alkane posses at any instance during petroleum refining. Qualitative Analysis: Provides information on how to identify an unknown sample during quality control. Reactor Design: Provides information to the engineer on how to build a chemical reactor for alkanes. Research: To expand the scope of inductive effect in organic chemistry. Also to prove that alkanes are not absolutely unreactive. The relative polarity and differences in electro negativities between the C-C and C-H bond which is 2.6 and 2.1 respectively makes electrons available for a conventional inductive effect (Arun 2009).

Chemical and Process Engineering Research ISSN 2224-7467 (Paper) ISSN 2225-0913 (Online) Vol.6, 2013
BIBLIOGRAPHY Ababio, Y (2001) New School Chemistry. Africana- F. E. P Publishers Limited. Singapore-ISBN-9971103982, PP.472, 80, 54-55

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Bahl, A.; Bahl, B. S; (2009) Advanced Organic Chemistry. S. Chand and Company Ltd. Ram Nagar, New Delhi 110 055, P. 201 Nelkon, M.; Parker, P.; (1995) Advanced Level Physics. C. B. S Publishers. 11, Daryaganj, New Delhi 110002(INDIA), pp. 54-55 Sharma, K .K.; Sharma, L.K; (2007) Physical Chemistry. Vikas Publishing House PVT LTD 576, Masjid road, Jangpura, New Delhi-110014 P.17 Joan Joseph Castillo (2009), Random Error [Online] Available: http://www.explorable.com Random error(copyright 2008-2012) Siddharth Kalla (2009), Random Error [Online] Available: http://www.explorable.com Random error (December 12, 2012) Jeffrey S Rosenthal (2012), University of Toronto, Canada. Infinite Dimensional Analysis, Quantum Probability Vol. 15 [Online] Available: http://www.worldscientific.com/ IdaqP (October, 2012) Gibbings, J. C. (2011, XIV, 297 P. 84 ), Mechanics Dimensional Analysis, an essential Scientific Method and a powerful Tool for Solving Problems in Physics. [Online] Available. http://www.springer.com.> Home >Materials > (November, 2011)

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