Carbon tetrachloride, dipole

The unequal distribution of charge produced when elements of different electronegativities combine causes a polarity of the covalent bond joining them and, unless this polarity is balanced by an equal and opposite polarity, the molecule will be a dipole and have a dipole moment (for example, a hydrogen halide). Carbon tetrachloride is one of a relatively few examples in which a strong polarity does not result in a molecular dipole. It has a tetrahedral configuration... 

This h)rpothesis has, however, been supported. The o p-ratio in chlorobenzene was found to be lower when acetic anhydride was the solvent, than when nitric acid or mixed acids were used. The ratio was still further reduced by the introduction into the solution of an even less polar solvent such as carbon tetrachloride, and was increased by the addition of a polar solvent such as acetonitrile. The orientation of substitution in toluene in which the substituent does not posses a strong dipole was found to be independent of the conditions used. The author... 

Carbon tetrachloride with four polar C—Cl bonds and a tetrahedral shape has no net dipole moment because the result of the four bond dipoles as shown m Figure 1 7 is zero Dichloromethane on the other hand has a dipole moment of 1 62 D The C—H bond dipoles reinforce the C—Cl bond dipoles... 

FIGURE 1 7 Contri bution of individual bond dipole moments to the mo lecular dipole moments of (a) carbon tetrachloride (CCy and (b) dichloro methane (CH2CI2)... 

In each case the left-hand atom of the pair as written is the least electronegative. Since dipole moments have direction as well as magnitude it is necessary to add the moments of each bond vertically. For this reason the individual dipole moments cancel each other out in carbon tetrachloride but only partially in chloroform. In other molecules, such as that of water, it is necessary to know the bond angle to calculate the dipole moment. Alternatively since the dipole moment of the molecule is measurable the method may be used to compute the bond angle. 

Nonpolar molecules such as H, N, O, I, and Cl have zero dipole moments, because e = 0. On the other hand, hydrogen fluoride, HF, has a large dipole moment of 1.75 Debye and so is strongly polar. Simple carbon compounds with symmetric arrangement of like atoms (e.g., methane, CH, and carbon tetrachloride,CCl.,) have zero dipole moments and so are nonpolar. 

Carbon tetrachloride, CCU, is another molecule that, like BeF is nonpolar despite the presence of polar bonds. Each of its four bonds is a dipole, C - — CL However because the four bonds are arranged symmetrically around the carbon atom, they canceL As a result, the molecule has no net dipole it is nonpolar. If one of the Cl atoms in CCI4 is replaced by hydrogen, the situation changes. In the CHCl3 molecule, the H - — C dipole does not cancel with the three C -)— Cl dipoles. Hence CHC13 is polar. 

Chloroform, CHCla, is an example of a polar molecule. It has the same bond angles as methane, CH4, and carbon tetrachloride, CCLi- Carbon, with sp3 bonding, forms four tetrahedrally oriented bonds (as in Figure 16-11). However, the cancellation of the electric dipoles of the four C—Cl bonds in CCL does not occur when one of the chlorine atoms is replaced by a hydrogen atom. There is, then, a molecular dipole remaining. The effects of such electric dipoles are important to chemists because they affect chemical properties. We shall examine one of these, solvent action. 

If the four atoms attached to the central atom in a tetrahedral molecule are the same, as in tetrachloromethane (carbon tetrachloride), CCI4 (30), the dipole moments cancel and the molecule is nonpolar. However, if one or more of the atoms are replaced by different atoms, as in trichloromethane (chloroform), Cl ICI, or by lone pairs, as in NH3, then the dipole moments associated with the bonds are not all the same, so they do not cancel. Thus, the CHCI, molecule is polar (31). 

At the opposite extreme, molecular solids contain individual molecules bound together by various combinations of dispersion forces, dipole forces, and hydrogen bonds. Conforming to like dissolves like, molecular solids dissolve readily in solvents with similar types of intermolecular forces. Nonpolar I2, for instance, is soluble in nonpolar liquids such as carbon tetrachloride (CCI4). Many organic compounds are molecular solids that dissolve in organic liquids such as cyclohexane and acetone. 

Because chlorine is more electronegative than carbon, carbon tetrachloride has four polar covalent bonds. But, as pointed out earlier, the molecular symmetry cancels out the electric dipoles of the individual bonds. The result is a nonpolar molecule. Like water, carbon tetrachloride is a good solvent. At one time, it was used as a dry cleaning agent. Water and carbon tetrachloride, however, dissolve entirely different classes of compounds. Carbon tetrachloride forms solutions with nonpolar organic compounds. It is infinitely miscible, for example, with benzene, whereas water and benzene do not mix. 

Compounds with high dielectric constants such as water, ethanol and acetonitrile, tend to heat readily. Less polar substances like aromatic and aliphatic hydrocarbons or compounds with no net dipole moment (e. g. carbon dioxide, dioxane, and carbon tetrachloride) and highly ordered crystalline materials, are poorly absorbing. 

According to the electrostatic model the solvation is due to electrostatic interaction between the charged ions and the dipolar solvent molecules. Thus the solvating and ionizing properties of a solvent are considered as being due primarily to the dipole moment of the solvent molecules. Thus, ionic compounds such as sodium chloride are insoluble in non-polar solvents such as carbon tetrachloride. Actually, rather than the dipole moment the field action of the dipoles should be considered. This approach might explain why acetonitrile (p = 3.2) is poor in its ionizing properties compared to water (p = 1.84). However, no numerical values are available for this quantity. 

If equal bond dipoles act in opposite directions in three-dimensional space, they counteract each other. A molecule with identical polar bonds that point in opposite directions is not polar. Figure 1.5 shows two examples, carbon dioxide and carbon tetrachloride. Carbon dioxide, CO2, has two polar C=0 bonds acting in opposite directions, so the molecule is non-polar. Carbon tetrachloride, CCI4, has four polar C—Cl bonds in a tetrahedral shape. You can prove mathematically that four identical dipoles, pointing toward the vertices of a tetrahedron, counteract each other exactly. (Note that this mathematical proof only applies if all four bonds are identical.) Therefore, carbon tetrachloride is also non-polar. 

Bond polarity in a molecule can often be measured by a dipole moment, expressed in Debye imits (D). However, the physical measurement provides only the overall dipole moment, i.e. the snm of the individual dipoles. A molecule might possess bond polarity without displaying an overall dipole if two or more polar bonds are aligned so that they cancel each other out. The C-Cl bond is polar, but although chloroform (CHCI3) has a dipole moment (1.02 D), carbon tetrachloride (CCI4) has no overall dipole. Becanse of the tetrahedral orientation of the dipoles in carbon tetrachloride, the vector sum is zero. 

Yellowish red oily liquid pungent penetrating odor fumes in air refractive index 1.670 at 20°C density 1.69 g/mL dipole moment 1.60 dielectric constant 4.9 at 22°C freezes at -77°C boils at 137°C reacts with water soluble in ethanol, benzene, ether, chloroform, and carbon tetrachloride dissolves sulfur at ambient temperature (67 g/100 g sulfur chloride). 

Water freezes to ice at 0°C expands by about 10% on freezing boils at 100°C vapor pressure at 0°, 20°, 50°, and 100°C are 4.6, 17.5, 92.5, and 760 torr, respectively dielectric constant 80.2 at 20°C and 76.6 at 30°C dipole moment in benzene at 25°C 1.76 critical temperature 373.99°C critical pressure 217.8 atm critical density 0.322 g/cm viscosity 0.01002 poise at 20°C surface tension 73 dynes/cm at 20°C dissolves ionic substances miscible with mineral acids, alkalies low molecular weight alcohols, aldehydes and ketones forms an azeotrope with several solvents immiscible with nonpolar solvents such as carbon tetrachloride, hexane, chloroform, benzene, toluene, and carbon disulfide. 

The dipole moment of 2,2 -bipyridine in benzene or carbon tetrachloride has been reported as less than 0.68, 0.91, 0.69, and 0.61 d. Because the conformation with the two nitrogen atoms transoid to each other should have a zero dipole moment and the cisoid configuration a value of 3.8 D, the consensus is that the molecule is in the transoid conformation and is approximately planar in solution with an angle of about 20° between... 

Molar Kerr constants mK and dipole moments squared of polytoxyethylene giycoils (POEG) and polyjoxyethylene dimethyl ether)s (POEDE) are reported in the isotropically polarizable solvents carbon tetrachloride, cyclohexane, and dioxane. Data for mK/x for POEG appear to reach an asymptotical value, Calculations of mK/x and /x based on the RIS model show good agreement with the experimental results. 

The dipole moments of molecules are often treated as being equal to the vector sum of the bond dipoles of the various bonds in the molecules. It is almost impossible to measure the dipole moment of an individual bond within a molecule. For example, molecules such as methane, carbon tetrachloride, and p-dichlorobenzene have no dipole moments, whereas molecules such as methylene chloride and m-dichlorobenzene do. The vector sum treatment could be made to agree quantitatively with all known dipole moments if the bond moments were treated as variables that depend on the nature of the particular molecule in which the bonds were located. 

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