Anoshan Indreswaran (13491) 1

Introduction
In 1690, the Swedish-German alchemist named Johann Kunckel von Lwenstern reacted mercury with nitric acid and alcohol to produced the compound Mercury fulminate, but he was unsuccessful in isolating it. However, later in 1799, the compound was studied by the English chemist Edward Howard, and he succeeded in isolating it. Further, he proposed it to be used as a trigger for explosives (Akhavan, 2004). Later in the 20th century, after Mercury Fulminate [Hg(CNO)2] was used by Alfred Nobel, in 1864, as an initiator in the metal blasting cap detonator to detonate dynamite [nitroglycerine], it was widely produced (Akhavan, 2004). The paper provides an overview into the physical properties, the bonding, the production, and the chemistry of the explosive and the products of mercury fulminate.

Mercury Fulminate
Mercury fulminate is an inorganic fulminate obtained through the reaction of mercuric nitrate solution with alcohol in nitric acid. Mercury fulminate is a crystalline solid of grey, pale brown or white in color. Its molecular formula is C2N202Hg, and it has a molecular weight of 284.63 gmol-1 (Beck, 2007).

fig. 1: mercury fulminate

Anoshan Indreswaran (13491) 2 Below is the structural formula of mercury fulminate.

The fulminate salt of most metals are ionic compounds, but, interestingly, the bond between mercury and the fulminate is covalent, that is the Hg - CNO bond. When you consider the bond in the fulminate ion, there is a triple bond between carbon and nitrogen, which is common in case of nitrogen to form triple bond to attain the octet electronic configuration in its outer most electron shell. However, besides having gained the octet electronic structure, nitrogen has formed a dative bond, sharing its remaining lone pair of electrons in the dative covalent bond between nitrogen and oxygen. Overall, every atom has reached the stable octet electronic configuration, but not the mercury. Yet, its not surprising that the transition metals do not necessarily form compounds to reach the noble gas configuration. In the molecule, since mercury is the central atom and its a metal, mercury has an oxidation number of +2, because it has bonded with 2 fulminate ions with oxidation number -1. In the fulminate ion, the oxidation state of oxygen is -2 because it has formed a double bond with nitrogen and it is the most electronegative atom in the ion. Next in the order of electronegativity comes the nitrogen, from the bonding with oxygen, nitrogen is labled with a plus to oxidation state, and considering the triple bond with carbon, the oxidation state is -3. In sum, the oxidation state of nitrogen in the molecule is -1. Thus, by balancing the remaining oxidation number of the fulminate ion and the oxidation number of the nitrogen, carbon and oxygen atom, carbon atom's oxidation number is calculated as +2. According to me, inferring from the Valence Shell Electron Pair Repulsion (VSEPR) Theory, the shape of the molecule should be linear because the central atom is surrounded by two bonding pairs on either side without any valence electron on the central atom. However, according to the article The

Anoshan Indreswaran (13491) 3 Crystal and Molecular Structure of Mercury Fulminate, the bond lengths of Hg-C, CN, and N-O are 2.029 , 1.143 , and 1.248 respectively. Further, the bond angles of the molecule are Hg-CN 169.1o, CN-O 179.7o, and C-Hg-C 180.0o, and as it is apparent that the bond angle deviates from 180.0o as we measure away from the central atom, that is mercury. Thus, the shape of the molecule is bent. Importantly, it should be noted that using the VSEPR theory, the geometry of this molecule cannot be determined (Beck, 2007). Bond length in Hg-C Hg[CNO]2 2.029 CN 1.143 N-O 1.248 Bond angle in degrees Hg-CN 169.1 CN-O 179.7 C-Hg-C 180.0

fig. 2: Bent shape of mercury fulminate. According to Beck, in the crystal structure of mercury fulminate, a central mercury atom is surrounded by 12 atoms: 6 Hg---O and 6 Hg---N weak van-der-Waals forces. fig. 3: Crystal structure of mercury fulminate.

I believe the mercury fulminate molecule is polar because, even though the fulminate ions on

Anoshan Indreswaran (13491) 4 either side of the mercury is expected to cancel the polar effect of the individual polar ions, due to the bent shape of the molecule, it is not possible as in the water molecule. However, I think, the bond between mercury and carbon is non-polar because the bond angle of the C-Hg-C is 180o and the pull from the fulminate ion from either sides are equal. In the fulminate ion, the nitrogen-oxygen bond has the electron cloud around the oxygen because of the high electronegativity of oxygen, and similarly in the carbon-nitrogen bond, the bond is polarized towards nitrogen. The crystal is of 4.42 g/cm3 [at 20 oC] density with a melting point of 160 oC and boiling point of 356.6 oC. Further, the compound undergoes thermal decomposition at 90 oC and thermal ignition at 170 oC. Energy of formation/kJ kg-1. The solubility of mercury fulminate in water is very low, but it is soluble in ethanol and ammonia (Beck, 2007).

Mercury Fulminate Production

First, dissolve mercury in nitric acid and then pour the mixture into ethanol. This is a vigorous reaction with the emission of white fumes, which is followed by brownish-red fumes, and at last again the emission of white fumes. At the same time, it could be observed that mercury fulminate crystals are being formed. Then take the crystals and wash it under water till all of the remaining acid is washed away. Finally, the remaining product is mercury fulminate [(CNO)2Hg]. The greyish color fulminate crystals should be stored under water (Akhavan, 2004). In the reaction, the white fumes and red fumes are caused by different compositions of the nitric acid. Nitric acid in its pure form gives out white fumes as we could observe initially, and finally when it is formed again in the final reaction. The red fume is formed in the intermediate stage where the nitric acid is reduced. During the reduction the dissolved nitrogen dioxide [2 HNO2 NO2 + NO + H2O] in the nitric acid is the cause for the red color fuming.

Anoshan Indreswaran (13491) 5 Mechanism of the reaction and the intermediate steps First, the ethanol is oxidized to ethanal by nitric acid and the products are ethanal, nitrous acid and water. CH3CH2OH + HNO3 CH3CHO + HNO2 + H2O Next is a nitrosation reaction; the nitrous acid and ethanal formed from the previous reaction reacts to form nitrosoethanol and water. CH3CHO + HNO2 NOCH2CHO + H2O Here, isomerization of nitrosoethanal to isonitrosoethanal takes place. The double bond in N=O breaks and O-H bond is formed; the H-bond is from the C-H. A C=N double bond is formed between the carbon atom, where the H-C bond was broken, and the nitrogen atom. NOCH2CHO HON=CH-CHO The acidity due to the presence of nitric acid, helps in the oxidation of the isonitrosoethanal to isonitrosoethanoic acid. HON=CH-CHO + H2O HON=CH-COOH + 2H+ + 2e Then, the isonitrosoethanoic acid decomposes to form fulminic acid and methanoic acid. HON=CH-COOH CNOH + HCOOH Finally, mercury fulminate is formed when the fulminic acid reacts with mercury nitrate. 2CNOH + Hg(NO3)2 (CNO)2Hg + 2HNO3

Anoshan Indreswaran (13491) 6

Mercury fulminate Explosive

An accumulation of energy in a space which is suddenly released results in an explosion; this can occur from the energy released by a chemical reaction, a physical transformation or an atomic change (Akhavan, 2004). Chemical explosions occur during a change of state or a chemical reaction within a short time and space which results in a very high and accelerated exothermic transformation, and usually a emission of a large amount of gas (Akhavan, 2004). Mercury fulminate falls under the fulminate explosive if classified according to molecular groups. When viewed from the point of view of performance and use, it is categorized as a primary explosive. It is a primary explosive because of its quick transformation from burning to detonation, and due to its ability to transform the detonation to less sensitive explosive. Further, either shock, heat, electric spark, or friction could detonate it whether it is confined or not, dissociating the molecule, and leading it to act as the trigger. Its sensitivity is reduced by adding water to it, yet because of its sensitivity to the sunlight, it decomposes giving out a gas (Akhavan, 2004). Mercury fulminate, on explosion, produces carbon monoxide, nitrogen, and mercury, which are stable compounds (Akhavan, 2004). Given below is the decomposition of Mercury fulminate on detonation (CNO)2Hg 2CO + N2 + Hg If we analyze the products, the reaction forms very stable elements and compounds. In mercury, there exists a metallic bond, and in the nitrogen gas its a triple bond which is covalent and non-polar. In

Anoshan Indreswaran (13491) 7 carbon monoxide, there are two covalent bonds and one dative bond formed by the electron from oxygen atom. It is polar molecule with a small negative charge on carbon and a small positive charge on the oxygen atom. When you consider the oxidation numbers, nitrogen and mercury is in the zero oxidation state, while in carbon monoxide, carbon has

Thermochemistry of Mercury fulminate

Thermochemistry is very important in understanding the energy change during a reaction, the kinetics of the reaction and the mechanisms. However, it is important to know that the theoretical calculations does not agree with the experimental results because of different experimental conditions (Akhavan, 2004). In an explosive reaction, the molecule splits into its constituent atoms and re-arranges itself to stable molecule/s in a fraction of time. Further, usually, the carbon atoms are oxidized to carbon dioxide and the hydrogen atoms are combusted to water molecules, nitrogen and several other stable molecules (Akhavan, 2004). (CNO)2Hg 2CO + N2 + Hg 2C + 2N +2O + Hg H
atm

(CNO)2Hg HR

Hform 2CO + N2 + Hg

fig. 4: Energy is used in breaking the bonds of the explosive, and then energy is released out during the formation of bonds.

Anoshan Indreswaran (13491) 8 Applying Hess's law to the above energy diagram, enthalpy of the reaction can be calculated. HR = Hatm + Hform The enthalpy of the reaction could be calculated as follows, assuming under standard conditions: HReaction = Hformation of products - Hformation of reactants HReaction = (2 X Hformation of CO + Hformation of Nitrogen + Hformation of Hg) - (Hformation of (CNO)-Hg-(CNO)) HReaction = 2 X (-110.0) + 0 + 0 386 (N.B.: The standard enthalpy of formation of elements in its most stable natural state is zero.) HReaction = -606 kJmol-1 H Reaction 1000 M

Q=

Q- Heat of explosion, M - Molecular mass

Q = 2129.1 kJkg-1 Therefore, the heat of the detonation reaction of mercury fulminate or the enthalpy of the reaction is -606 kJmol-1 and the heat of explosion is 2129.1 kJkg-1. In addition, since the enthalpy of the reaction is negative, we can conclude that the reaction is exothermic. According to Akhavan, the heat of explosion and heat of detonation at constant volume for the fulminate is -500 kJmol-1 and 1755 kJkg-1. The power index of an explosive is stated as a percentage relative to the standard explosivepicric acid. The explosive power is the product of the volume of gas and the heat of explosion. The power index of fulminated mercury is 14% (Akhavan, 2004).

Anoshan Indreswaran (13491) 9

Kinetics of the Reaction

Kinetics is the subject about the rate of change of a reaction. In case of explosives, the rate of change is very high and depends on the concentration of the reactants, temperature and the pressure of the reaction (Akhavan, 2004). During the decomposition of mercury fulminate, if the activation energy supplied is not sufficient then the reaction does not take place. Instead, when sufficient energy is provided the reactions moves forward forming the products and releasing energy to the system (Akhavan, 2004).

fig. 5: Energy vs Reaction progress graph of a typical exothermic reaction. From the above diagram it is clear that to successfully complete the reaction, sufficient Ea (i.e. activation energy) should be provided, then the resulting release in energy from the reaction is depicted in the diagram as H (Akhavan, 2004). The rate of a reaction is determined by the magnitude of the activation energy and the temperature of the reaction. It is given by the Arrhenius equation: k = A e -E/RT k- constant for the rate of reaction

Anoshan Indreswaran (13491) 10 A- collision factor (constant for a given material) E-activation energy in Jmol-1 R- universal gas constant (8.314 Jmol-1K-l) T- temperature in Kelvin The activation energy of mercury fulminate is 105 kJmol-1 and the collision factor is 1011. The primary explosives have low value for activation energy and collision factor making the reaction require less energy to start. This property makes the primary explosives very sensitive, even exploding due to the energy formed by friction. This explains the high sensitivity of mercury fulminate (Akhavan, 2004). Conclusion In conclusion, mercury fulminate is a highly unstable polar molecule in crystalline structure, with weak van-der-Waals forces between the molecules, which was highly used in the past as a primary explosive due to its high sensitivity. The compound detonates even by the slightest energy introduced by friction. It is stored underwater because of its higly decomposable nature, and on decomposition, carbon monoxide, nitrogen and mercury are obtained.

Anoshan Indreswaran (13491) 11

Reference Akhavan, J. (2004). The chemistry of explosives (2nd ed.). Cambridge, UK: Royal Society of Chemistry.

Beck, W., Evers, J., Gbel, M., Oehlinger, G. and Klaptke, T. M. (2007). The Crystal and Molecular Structure of Mercury Fulminate (Knallquecksilber). Z. anorg. allg. Chem., 633:14171422.

Clark, J. (2004). OXIDATION OF ALDEHYDES AND KETONES. http://www.chemguide.co.uk/organicprops/carbonyls/oxidation.html Iqbal, Z. and Yoffe, A. D. (n.d.). Electronic Structure and Stability of the Inorganic Fulminates.