Absorption of nitrogen oxides has been extensively studied, in the concentration range higher than several per cents

in an absorption tower to produce nitric acid, in the concentration range of parts per million volume basis in tail gas purification, in the concentration range of parts per billion volume basis in atmosphere producing acid rain droplets.

1 reactions Oxidation reactions (what are possible products between N-O?) NO and NO2 are dominant species from combustion. R1: R2: R3: R4: R5: R6: 2NO+O2=2NO2 (reversed reaction R6?) NO+NO2=N2O3 2NO2=N2O4 2NO2+1/2O2=N2O5 (reversed reaction N2O5=NO2+NO3?) NO3+NO2->NO+NO2+O2 [1],[2] (whether product can be N2O5?) NO3+NO->2NO2 [1] (What is product of decomposition of NO3?)

H2O absorption reactions, absorption depends on the concentration of nitric acid, especially R6 and R9. R7: R8: NO+H2O=? 3NO2 (or N2O4)+H2O=2HNO3+NO [3],[4]

The reaction in the gas phase is studied. [5] The absorption of nitrogen peroxide in water to form nitric acid with the simultaneous liberation of nitric acid is the fundamental reaction taking place in the absorbing tower. This mechanism takes place with dilute nitric acid, not in concentrated nitric acid. The gas phase equilibrium depends on the nitric acid concentration. The direct determination of equilibrium is limited to solutions containing between 10 and 55% nitric acid. In the case of solutions below 10%, the partial pressures of nitrogen peroxide became too small; in the case of solutions above 55%, the partial pressure of nitric oxide became too small. The ratio of NO to NO2 is 10^5 when the concentration of nitric acid was 1.1%, and 10^-7 when the concentration was 65.3%. [3] In a flat surface absorber and bubbling absorber, the absorption rates of NO2 depend on the concentration of NO2 in second order at the concentrations above around 800 ppm, 3/2 order in NO2 at the lower concentrations, then 1 order at rather large mass transfer coefficient. [6] The assumption that N2O4 is transporting species. The liquid analysis indicates NO2- and NO3- produced in liquid has equal molar concentrations. [6] R8: NO+2HNO3=H2O+3NO2

The reaction is heterogeneous; species of NO, NO2, HNO3, H2O were identified in the gas phase by IR. Rate coefficient of 8.4 L/mol-s is obtained. [7]

R9:

2NO2+1/2O2+H2O=2HNO3 [4]

The reaction combining R1 and R8, is very slow in the gas phase. [4] (Maybe the rate is limited by NO oxidation step, introducing O3 is one way to enhance oxidation [8])

R9:

2HNO3=2NO2+1/2O2+H2O

Ref [9] studied the reversible reaction. During the decomposition, pressure is developed.

R10:

N2O3 (or NO+NO2) +H2O=2HNO2 [6]

The absorption rates change in order with respect to the product of NO and NO2. N2O3 is considered to be reactive and transporting species. NO3- concentrations were negligibly small compared with NO2-. [6] R10: 2HNO2 and 3HNO3=HNO3+2NO+H2O

R11:

N2O5+H2O=2HNO3 [8],[10]

Homogeneous gas-phase reaction, N2O5, HNO3 and H2O was analysed using FTIR, N2O5 was prepared by mixing NO2 with excess O3 in purified air. [8] N2O5 forms only nitrate ions in the NaOH solution, with close to 100% efficiency. [8]

HNO3 absorption reactions R12: 2NO+HNO3+H2O=3HNO2 [3],[11],[12]

Absorption of NO into nitric acid takes place if solution is concentrated. [3] The reaction has been studied in the gas phase. [13]

R13:

NO2+HNO3[14]

R14:

HNO2+HNO3= 2NO2+H2O

The reaction in the gas phase is studied in Ref. [15]

Alkali absorption Absorption of nitrogen peroxide in alkali gives equimolal mixture of nitrate and nitrite, only when the absorption takes place in the absence of oxygen. Absorption of equimolal mixture of nitrogen peroxide and nitric oxide gives pure nitrite. [3] Absorption of N2O5 gives nitrate only. [8]

Physical chemical data Nitric acid-H2O mixture [16], Vapour pressure in HNO3 acid:[17],[18],at low temperature [19] Nitric acid-nitrogen dioxide mixture[16],

NO2-HNO3-H2O ternary system [20],[21],[22],[23]: NO2 dissolves into nitric acid and can reduce the bubbling point. Vapour pressure in NO-NO2-HNO3 system: HNO3 [3],[24], NO [3],[25] NO2 [3],[24],[25] N2O4 [3]

2Nitric acid manufacture: (context 1) Oxidizing N2 to its oxides is a major route to fix molecular nitrogen from atmosphere by industrial process. The thermal method to produce oxide via N2+O2=2NO is of low efficiency. Processes developed in nitrogen industry generally adopt Haber process to produce ammonia N2+3H2=2NH3.

Ammonia combusts with oxygen form NO. Under low temperature and high pressure, NO is further oxidized to NO2, which is absorbed by H2O to form nitric acid. This is so called Ostwald process.

Haber process Ammonia is produced basically from water, air, and energy. The energy source is usually natural gas, hydrocarbons liquid fuels, and solid coal. The total energy consumption for the production of ammonia in a modern steam reforming plant is 40-50% above the thermodynamic minimum. More than half of the excess consumption is due to compression losses.

Steam reforming of natural gas is the most efficient route, with about 77% of world ammonia capacity being based on natural gas. The synthetic gas production and purification normally take place at 25-35 bar. The feedstock is preheated to 350-400C and treated in a desulphurisation vessel. Then the gas is mixed with steam to 500-600C, at steam to carbon molar ratio around 3. At the main reformer section, temperature is raised to 780830 C. Only 30-40% of the hydrocarbon feed is reformed in the primary reformer, the rest was fed into secondary reformer. The reformer outlet temperature is around 1000C, then cooled to 350-400C in a waste heat steam boiler. The shift reaction in high temperature shift convertor (HTS) operating around 400C and the low temperature shift converter (LTS) operating around 200-220C converts CO to CO2. The CO2 is removed in a chemical or a physical absorption process. The rest CO is removed in a methanation reactor at 300C. The ammonia is synthesized in the range 100-250 bar and 350-550C. Only 20-30% is reacted per pass, the rest is recycled by cooling/condensation. Ammonia is condensed by cooling water, cooling air, or ammonia refrigerant. [26]

Figure 1 Flow sheet for ammonia production [26]

Ostwald process All plants for the product of nitric acid are currently based on the same basic chemical operations: 1. Oxidation of ammonia with air to give nitric oxide; 2. Oxidation of the nitric oxide to nitrogen dioxide and absorption in water to give a solution of nitric acid. The efficiency of the first step is favoured by low pressure and that of the second step is favoured by high pressure. The main unit operations are air filtration, air compression, air/ammonia mixing, air/ammonia oxidation over catalytic gauzes, energy recovery by steam generation and/or gas re-heating, gas cooling, gas compression, energy recovery and cooling, absorption, tail gas heating, energy recovery by expansion of the waste gas to atmosphere in a gas turbine.

Figure 2 Flow sheet for nitric acid production [27] Ammonia reacts with air on catalyst: 4NH3 + 5O2 = 4NO + 6H2O 4NH3+ 3O2 = 2N2 + 6H2O 4NH3+4O2=2N2O + 6H2O The NO yield (%) depends on temperature and pressure. To achieve similar yield, temperature should increase as pressure increases. The gas is cooled to 100 to 200 C by cooling water. By adding extra oxygen into a counter-current flow absorber, NO2 is formed and absorbed. These reactions are favoured by higher pressure and lower temperature. Because the reaction is exothermic, so that continuous cooling is required. It is noted that nitric acid product contains dissolved nitrogen oxides. The nitric acid production has been simulated thermodynamically. [28] (I would not use his strategy to apply thermodynamics in such a manner)

Thermodynamic systems relevant to condensed phase are H2O, HNO2 and HNO3. [29]

[29]

3 Acid rain mechanism (context2) 1 What is acid rain? Acidity of rain is indicated by its pH value. Clean rain water should have a pH value of about 5, any measured pH under 5 is considered as acid rain. [30] (I would put a question mark on pH=5). Due to the presence of carbon dioxide in the air, the pH of rain droplets is close to 5.6 in equilibrium with 360ppm carbon dioxide. In a recent study, rain with pH>5.6 is defined as not acid, 4.5<pH<5.6 is as gentle acid, pH<4.5 as strong acid. [31] At pH of 4.5, molecular sulphur dioxide starts to form; in another word rain is saturated with sulphur dioxide. Adding sodium carbonate into rain samples to raise pH value close to 10 was practised to retain molecular carbon dioxide in rain samples. [32] A study found pH of rain samples increased during storage, but pH can be kept at constant if chloroform was added. [33] (Here I would ask one question, at the same amount of sulphur and nitrogen, whether sulphate is more acidic than sulphite? Whether nitrate is more acidic than nitrite? The answer is expected to be YES) Acid rain is composed of anions and cations, and other solids. It is considered some organic acid such as formic acid and acetic acid also present in acid rains. [33] A typical acid rain analysis indicates pH value, conductivity, nitrate, sulphate, chloride, fluoride etc ion concentrations, and NH4+, Na, K, Mg, Ca cations and other trace elements. [32],[33],[34]

There is an inverse correlation between ionic concentrations and rainfall amount (in millimetre), so-called dilution effect, with higher concentrations tend to be associated with low intensity rainfalls while intense rainfalls tend to have low concentrations. [33] (implication for scrubber system is by changing gas-liquid ratio, the ratio of different ion concentrations is a constant) The interrelationships between anions and cations have been studied attempting to interpret the origins of acid rain. For example, a strong correlation between sulphate and nitrite has been found. [32],[33]
2.5

2
NO3-, ppm

1.5

0.5

0 0 1 2 3 4 SO4-, ppm 5 6 7

Figure 3 Data from Ref. [32] Several studies have found decreasing trends in the concentrations of SO4-- due to the decrease of SO2 emissions from a local resource. Also there is a noticeable trend for increasing NO3-. [34]

SO2 emission in china [35]

2 Acid rain in Australia. Serious or not? Air quality in Australia is guided by the National Environment Measurement (AAQ NEPM) which was made in 1998 and formally commenced in 2002. It monitors ozone, PM, CO, NO2, SO2, and lead. In addition to the AAQ NEPM, Australia established a National Environment Protection Air Toxics Measure in 2004 for monitoring benzene, toluene, xylene, formaldehyde and benzo(a) pyrene. Sulphur dioxide levels across Australian cities have remained fairly steady over the last decade. Nitrogen dioxide levels remained fairly steady in the last decade, while peak concentrations declined quite significantly in the last two decades. The drop is mainly due to the improved emission controls on motor vehicles. While in USA, the SOx and NOx in the air keep declining in the last few decades.

The level of acid rain in most of Australia is low compared to other parts of the world, because Australian coal is very low in sulphur. In Australia, Kakadu National Park in the Northern Territory produce very high levels of acid rain at the start of each wet season. These levels are as acidic as parts of the Northern Hemisphere, but are caused by emissions from native tropical plants, rather than through any sort of human activities. [30] 3 Acid rain mechanism [36] Acid rain is a result of multiple variable interactions; the occurrence of acid rain depends on geographic location, terrain characteristics, routinely monitored meteorological factors, and column concentrations of atmospheric SO2 and NO2. The decision tree model simulation analysis indicated the significance of factors following the order of location, elevation, wind direction, wind speed, rainfall amount, atmospheric pressure, and precursors of acid rain. [31] The acidification of rain is principally due to the oxidation of SO2 or NOx in cloud droplets and raindrops, the absorption of free gaseous acids by droplets and raindrops, or scavenging of acid aerosol by the falling raindrops. [37]

Figure 4 A whole picture of acid rain [36] The rate of absorbing SO2 and NO2 into rain droplets can be described by mass transfer model of water droplet. However, there is great uncertainty in chemical scheme. A physico-chemical subcloud rain model is presented to simulate the effect of gaseous SO2, NO, NO2, HNO3, O3 and CO2 on rain acidity. It assumes dissolved SO2 is oxidized by O3. The aqueous chemistry of NOx species is not well known. Results indicated reduced absorption of SO2 if HNO3 present. (How its relevance to current oxy-fuel compression experiments? Sulphur-nitrogen interactions? ) [37] SO2 and NO2 concentrations can be obtained from existing ground-based data, aircraft observational data, and satellite data. (satellite data for Australian might available http://aura.gsfc.nasa.gov/instruments/omi/index.html)

The chemical mechanism for acid rain presented in Ref [36]: In the presence of water, sulphur trioxide is converted rapidly to sulphuric acid: SO3+H2O(l)=H2SO4(l); sulfur dioxide dissolves in water, hydrolysing in a series of equilibrium reactions: SO2+H2O(l)=H2SO3=H+ + HSO3- = 2H+ + SO3-Nitrogen dioxide reacts with OH to form nitric acid: NO2+OH=HNO3 (The chemical component and external conditions in atmosphere differs to the industrial conditions. Ozone, hydrogen peroxide, and hv play an important role on acid gases oxidation in the atmosphere, one important input from environment study relative to Tims work should be recent development in air monitoring instruments which monitor species such as HNO2 and HNO3 in the gas phase)

4 Knowledge gap: on chemical scheme The rain ionic analysis also indicates nitrate and sulphate are the predominant ions. But as we know, the main components emitted from fossil fuel combustion are composed by SO2 S(IV) and NO N(II), instead of S(VI) in SO4-- and N(V) in NO3-.

Why? The oxidation of sulphur and nitrogen play a critical role in acid rain mechanism. At present, the mechanism leading to HNO2 formation are still not completely understood. How? Homogeneous or heterogeneous mechanism? Or catalytic effect on aerosol surface?

Appendix: Nitric gases analysis methods 1 Introduction The thermodynamic system of N-O includes several nitrogen oxides, i.e. NO, NO2, N2O4, N2O, N2O3, N2O5, and NO3. In the H-N-O thermodynamic system, with HNO2 and HNO3 present additionally. The methods to identify these components are composed by sampling-offline analysis methods and online analysis methods. The typical sampling followed by offline analysis methods are given by Environmental Protection Agency (EPA) in the United States, such as Method 7 and its modified versions. The online analysis methods consist of electrochemical analysis (conductivity, colorimetry etc) and spectroscopic methods (UV, Vis, IR, GC, MS, RS etc).

2 Sampling-online analysis methods 2.1 Sampling into solution by absorption: Hydrogen peroxide method: Total fixed nitrogen in a gas sample is based on the oxidation of the nitrogen oxides with hydrogen peroxide and the subsequent titration of the nitric acid formed with a standardized solution of sodium hydroxide. [38] Modified Griess-Ilosvay method [38] Mixed acid (H2SO4-HNO3) method: mixed acid method involves the reaction of the nitrogen oxides with a mixed acid of nitric acid and sulphuric acid to form nitrososulfuric acid, which is then hydrolyzed to nitrous acid and oxidized to nitric acid by potassium permanganate. [38] Phenoldisulfonic acid method, EPA Method 7: the reference method for measurement of NO+NO2 emission from nitric acid plant. In this method, a sample is collected with evaluated 2-L flask over approximately 15 seconds period. This method is sensitive in the range of 5 ppm to several thousand ppm of total nitrogen oxides. [39],[40] Alkaline-permanganate collection solution, A-P method: uses 0.25M KMnO4-0.5M NaOH solution in three restricted-orifice impingers connected in series. MnO4- is reduced to MnO2 which is removed by filtration. [39] Saltzman method: requires quantitative conversion of NO to NO2. This method is sensitive below several ppm of nitrogen dioxide. 2.2 Followed by liquid analysis: Titration [38]

Ion Chromatograph [39] Colorimetry Conductometric method [11],[41]

3 Online analysis methods 3.1 Sampling into gas phase HNO3 is lost due to interaction with tube materials. It found sampling of ppb level HNO3 from atmosphere has problem with HNO3 adsorption onto materials. Less than 5% of HNO3 is adsorbed on Teflon fluoropolymer tubing (TFE Teflon, PFA Teflon, FEP Teflon, PVDF) after 1 min of HNO3 exposure, whereas >70% is lost on walls made of 304 stainless steel, glass, fused silica, 6061 aluminium, nylon, silica-coated steel, and silanecoated glass. [42] Nylon filter quantitatively scrubs HNO3.[43] HNO3 is easy to loss onto the glass walls, the problem can be overcome by using an all Teflon inlet. Nonzero humidity is preferred to avoid HNO3 loss. [44]

3.2 Followed by instrumental gas analysis: 3.2.1 Gas chromatograph Gas chromatograph: a gas mixture of N2, CO, CO2, NO, N2O was analysed with gas chromatograph. It is noted that differentiate NO/CO, N2O/CO2 has difficulty. [45]

3.2.2 Mass spectrometry: CIMS Chemical Ionization mass spectrometer (CIMS): is used for ppbv level HNO3 analysis. [42],[46]

3.2.3 Chemiluminence Chemiluminence[47], [48],[49],[44]: The principle is NO2 can be thermally dissociated to NO, NH3 can be oxidized to NO, then NO reacts with O3 to give a detectable light emission. Dissociation of NO2 begins at about 150C and is complete at about 620C. [47] In another study, a molybdenum catalyst operating in the 400 500 C temperature range is employed in the NOx channel. [43] The third body quenching reaction determines the chemiluminescent intensity.[49] To produce calibration HNO3 vapour, permeation tube is used. [46] Temperature and pressure controlled KinTek permeation tube. The permeation source flow is mixed with 1 slpm of dry synthetic air to produce a 5.6 ppbv HNO3. [42] In experiments, a method using HCl(g)+AgNO3(s)=HNO3(g)+AgCl(s) produces HNO3 at 20C. [EST1989] Nitric acid is prepared from dried potassium nitrate and concentrated sulphuric acid. [Smith1947] 3.2.4 Ultra Violet The wavelength of 1.4um was used to determine concentration of HNO3 vapour. [4]

3.2.5 Infrared spectrometry A gas mixture of NO, NO2, N2O4 and nitric acid vapour has been determined by infrared spectrometry. At higher concentrations of HNO3, the nitric acid vapour strongly overlaps the N2O4 absorption band. In gas mixture containing nitrogen oxides and water, nitrous acid vapour could be detected, especially at high NO/NO2 ratios. Nitric acid vapour was detected only in the gas sample at rather low NO concentration compared to the NO2 concentrations. [50]

[50]

3.2.6 TDLAS

3.2.7 EPR

3.2.8 DOAS Quantitative measurements of gas phase nitrous acid in ambient air were performed for the first time by Perner and Platt (1979) using Differential Optical Absorption Spectroscopy (DOAS). 4 Recommendations Start from methods in section 3.1, then use methods in section 3.2. Analytical techniques are gas phase and liquid phase are summarized below: Table 1 Gas phase analysis Titration GC IR UV Chemiluminescence TDLAS QMS Chemical ionization mass spectrometer (CIMS)

N2 [45] N2O [45] * NO [38] NO2 [38] HNO3 * [46] * HNO2 CO [45] CO2 [45] Tunable diode laser absorption spectroscopy (TDLAS) ,Quadrupole mass spectrometer (QMS) Table 2 Liquid phase analysis

Titration NO2+ NO3HNO2 HNO3 Reference

Ion Chromatograph (IC)

Raman Spectra * *

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