ammonia | 15123-00-9

• 分子结构分类: 无机化合物 - 均质非金属化合物 - 均质其他非金属化合物
• 英文名称: ammonia
• 英文别名: Ammonia-d1
• CAS: 15123-00-9
• 化学式: H₃N
• 分子量: 18.0226
• InChiKey: QGZKDVFQNNGYKY-DYCDLGHISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  1
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  ammonia 以 gaseous matrix 为溶剂， 生成 氢气 、 deuteroimine
  参考文献：
  名称：

  Photodissociation dynamics of à state ammonia molecules. II. The isotopic dependence for partially and fully deuterated isotopomers

  摘要：

  The technique of H(D) Rydberg atom photofragment translational spectroscopy has been used to investigate the photodissociation dynamics of the mixed isotopomers NH2D and NHD2 following the excitation to the v2′=0 and 1 levels of their lowest lying Ã 1B1 (C2v) excited electronic states. Peaks in the resulting total kinetic energy release (TKER) spectra are assigned to levels of the NH2, NHD, or ND2 fragments with a wide range of quantum numbers Ka for rotation about their a inertial axes, and with N=Ka, N=Ka+1, or N=Ka+2 as appropriate. These data provide the first measurements of high rotational levels for the ground electronic state of the NHD radical. The least squares fitting of all these spectra, and those resulting from NH3 and ND3, to the best calculated NH2, NHD, and/or ND2 rotational term values provides accurate estimations of the respective N–H and N–D bond dissociation energies D00 across the whole series. These values are D00(H–NH2)=37 115±20 cm−1 (4.602±0.002 eV); D00(H–NHD)=37 240±50 cm−1; D00(H–ND2)=37 300±30 cm−1; D00(D–NHD)=37 880±60 cm−1; and D00(D–ND2)=38 010±20 cm−1. The differences between these values are fully consistent with differences in zero-point energies and lead to a mean value of De=40 510±25 cm−1. Dissociation of NH2D or NHD2 through their (Ã−X̃) 210 bands to give an NHD product leads to TKER spectra with a much higher statistical character than those leading to an NH2 or ND2 product, and to those obtained following excitation through the 000 bands. This is rationalized in a semiquantitative manner in terms of a varying contribution to the dissociation rate of the parent molecules from internal conversion (IC) to high levels of their respective ground states. Nuclear permutation symmetry appears to play an important role both for the IC rates and for the subsequent branching between product channels.

  DOI：

  10.1063/1.471368
• 作为产物：
  描述：

  氨-d3 在 氨 作用下， 以 neat (no solvent) 为溶剂， 生成 ammonia
  参考文献：
  名称：

  用于激光同位素分离的双分子自由基清除过程：NH 2 D + O 2

  摘要：

  观察到NH 3 D混合物中NH 2 D的红外多光子光氧化仅产生HDO，表明一步分离氘的效率为[D 2 O] /（[D 2 0] + [H 2 O]）⩾50％，这是明显高于理论值的33％。结果由大速率的差异在自由基清除步骤所解释的，即ķ（d + O 2）= 2.2×10 9中号-1小号-1，ķ（NH 2 + O 2）⩽5×10 6中号- 1 s -1和k（NH 2 + NH 2）＝ 1.6×10 10 M -1 s -1。用钛固体粉末作为催化剂，我们观察到HDO的形成产率比不使用催化剂的HDO形成产率高至少三到四倍。

  DOI：

  10.1016/0009-2614(86)80294-9

文献信息

• An infrared study of lithium-ammonia and potassium-ammonia complexes trapped in solid argon
  作者：A. Loutellier、L. Manceron、J.P. Perchard

  DOI：10.1016/0301-0104(90)90016-3

  日期：1990.9

  and Li or K atoms in solid argon led to the spontaneous formation of numerous products classified in three groups. The first group is constituted by mononuclear species M(NH3)n mainly characterized by the strongly intensity enhanced ν1 (A1 stretching) and ν2 (A1 bending) modes of ammonia. For M=Li and n=1, 6Li/7Li and H/D, isotopic substitution allows complete assisgnment of the spectrum and force

  固态氩中氨和Li或K原子的冷凝导致自发形成许多分为三类的产物。第一组是由单核物种M（NH构成3）ñ主要呈现强烈强度增强ν 1（A 1拉伸）和ν 2（A 1弯曲）氨的模式。对于M = Li和n = 1、6 Li / 7 Li和H / D，同位素取代可以完全确认光谱并进行力场计算。用于增加值Ñ中，ν的频率降低1该模式表明与1：1络合物中的电子转移相反，即从M向氨分子转移，这对应于碱金属原子在液态氨中的稀溶液所描述的情况。第二组包括物种几个金属原子和一个氨分子，其中ν 1模式也红了相对于移动到其位置在1：1的复合物。由于预期电子传输的趋势与1：1情况（从氨向金属簇）相同，因此可以得出这样的结论：从M到氨（1：n种）或从氨对M（m：1种情况）引起相同的振动扰动。最后，在两个掺杂剂浓度高，所述光谱变化，主要是在ν特征在于谱带增宽1和ν 2个的光谱区域，不容易解释。
• Bond-selective photodissociation of partially deuterated ammonia molecules: Photodissociations of vibrationally excited NHD2 in the 5νNH state and NH2D in the 5νND state
  作者：Hiroshi Akagi、Keiichi Yokoyama、Atsushi Yokoyama

  DOI：10.1063/1.1645512

  日期：2004.3.8

  overtone state of the NH stretching mode (5nu(NH)) and NH(2)D excited to that of the ND stretching mode (5nu(ND)) has been investigated by using a crossed laser and molecular beams method. Branching ratio between the NH and ND bond dissociations has been determined by utilizing a (2+1) resonance enhanced multiphoton ionization scheme of H and D atoms. For the photolysis of NHD(2) in the 5nu(NH) state, the

  NHD（2）激发到NH拉伸模式（5nu（NH））的第四泛音态和NH（2）D激发到ND拉伸模式（5nu（ND））的第四泛音态的紫外光解离已经通过使用交叉激光和分子束法。NH和ND键解离之间的支化比已通过利用H和D原子的（2 + 1）共振增强多光子电离方案确定。对于处于5nu（NH）状态的NHD（2）的光解，每个键的NH解离截面是ND解离截面的5.1 +/- 1.4倍。另一方面，对于5nu（ND）状态的NH（2）D的光解，每个键的NH离解截面与ND离解截面的比值降低至0.68 +/- 0.16。与振动未激发的NH（2）D和NHD（2）的光解的分支比相比，本研究结果表明，NH拉伸模式的激发增强了NH与ca的离解。NH / ND支化比大两倍，而ND拉伸模式的激发导致ND与ca优先解离。ND / NH支化比是振动基态的3-4倍。从波包的能量学和动力学方面讨论了键选择增强的机理。ND / NH支化比是
• The Four Isotopomer Reactions of NH(<i>a</i>) and ND(<i>a</i>) with NH₃(<i>X̃</i>) and ND₃(<i>X̃</i>)
  作者：L. Adam、W. Hack、Matthias Olzmann

  DOI：10.1524/zpch.218.4.439.29201

  日期：2004.4.1

  The reactions

  NH(a) + NH₃(X̃) → products (1)

  ND(a) + NH₃(X̃) → products (2)

  NH(a) + ND₃(X̃) → products (3)

  ND(a) + ND₃(X̃) → products (4)

  were studied in a quasi-static reaction cell at room temperature and pressures of 10 and 20mbar with He as the main carrier gas. The electronically excited reactants NH(a) and ND(a) were generated by laser-flash photolysis of HN₃ and DN₃, respectively, at λ = 308nm and detected by laser-induced fluorescence (LIF). Also the ground state species NH(X) and ND(X) as products were detected by LIF.

  From the measured concentration-time profiles of NH(a) and ND(a) under pseudo-first order conditions, the following rate constants were obtained:

  NH(a) + NH₃(X̃) → products (1)

  ND(a) + NH₃(X̃) → products (2)

  NH(a) + ND₃(X̃) → products (3)

  ND(a) + ND₃(X̃) → products (4)

  k ₁ = (9.1 ± 0.9) × 10¹³ cm³mol⁻¹s⁻¹

  k ₂ = (9.6 ± 1.0) × 10¹³ cm³mol⁻¹s⁻¹

  k ₃ = (8.0 ± 1.0) × 10¹³ cm³mol⁻¹s⁻¹

  k ₄ = (7.2 ± 0.8) × 10¹³ cm³mol⁻¹s⁻¹.

  The major products are the corresponding NH _i D_{2 − i} (X̃) radicals (i = 0, 1, 2), whereas quenching processes such as NH(a) + ND₃ → NH(X) + ND₃ are of minor importance (1%). The isotope exchange NH(a) + ND₃ → ND(X) + NHD₂ is negligible, and the corresponding channel on the singlet surface NH(a) + ND₃(X ^~) → ND(a) + NHD₂(X̃) contributes with 1% to the overall NH(a) depletion in that reaction. The experimental findings are discussed in terms of a chemical activation mechanism by means of statistical rate theory.

  摘要：在室温和10到20mbar的压力下，在He作为主要载气体的条件下，通过激光闪光光解HN3和DN3生成电子激发态反应物NH(a)和ND(a)，并通过激光诱导荧光(LIF)进行检测。同时，通过LIF检测到了NH(X)和ND(X)作为产物的基态物种。 通过伪一级条件下测量的NH(a)和ND(a)浓度-时间曲线，得到了以下速率常数： k1 = (9.1 ± 0.9) × 10^13 cm^3mol^-1s^-1 k2 = (9.6 ± 1.0) × 10^13 cm^3mol^-1s^-1 k3 = (8.0 ± 1.0) × 10^13 cm^3mol^-1s^-1 k4 = (7.2 ± 0.8) × 10^13 cm^3mol^-1s^-1. 主要产物是相应的NH_iD_2−_i(X̃)自由基(i = 0, 1, 2)，而NH(a) + ND3 → NH(X) + ND3等猝灭过程的重要性较小(1%)。同位素交换NH(a) + ND3 → ND(X) + NHD2可以忽略不计，而在单线态表面NH(a) + ND3(X̃) → ND(a) + NHD2(X̃)通道对整体NH(a)耗尽的贡献为1%。实验结果通过统计速率理论讨论了化学活化机制。
• Steady-state isotopic transient-kinetic analysis of iron-catalyzed ammonia synthesis
  作者：J NWALOR

  DOI：10.1016/0021-9517(89)90225-x

  日期：1989.5

  Steady-state isotopic transient-kinetic analysis of ammonia synthesis catalysis has been conducted over a commercial Fe catalyst (Haldor Topsøe KMIR) permitting, for the first time, direct determinations of coverages in reactive intermediates of the working catalyst surface and assessments of the reaction mechanism and surface heterogeneity at steady-state reaction conditions. The reaction was studied

  氨合成催化的稳态同位素瞬态动力学分析已在商用铁催化剂（HaldorTopsøeKMIR）上进行，这首次允许直接确定工作催化剂表面反应性中间体的覆盖率并评估反应机理。和稳态反应条件下的表面异质性。将反应物的温度范围内623-773ķ了研究，在204或513千帕的总压力，以及用于ħ 2 / N 2在不存在H比3.化学吸附二氮的2还通过瞬态动力学技术在773 K下测量。结果表明，* N是最丰富的反应中间体。如所预期的，可以推断出在动力学上重要的反应步骤存在于反应路径上，随后是氮气。氢似乎增强了该步骤，该步骤似乎涉及二氮离解。观察到工作表面相对于合成反应是异质的。在204 kPa和623和673 K的温度下的稳态同位素瞬态曲线表明，一个主要的含氮表面中间体库。在723和773 K处，可能是由于先前休眠或饱和位点的活化或本体相氮物质的可能贡献，导致了第二个反应性较低的中间体库的形成。N-中间体的两个
• Ammonia adsorption on the Pt(111) AND Pt(S)-6(111) × (111) surfaces
  作者：John L. Gland、Edward B. Kollin

  DOI：10.1016/0039-6028(81)90073-x

  日期：1981.3

  of solid ammonia desorb in a narrow peak at 100 K. The weakly chemisorbed high coverage-low temperature form of molecular ammonia desorbs at 150 K with first order kinetics and a heat of desorption of 36 ± 3 kj mol (8.6 ± 0.6 kcal mol ) . The chemisorbed low coverage-high temperature form of molecular ammonia desorbs in a broad peak in the 170 to 450 K temperature range. Steady-state ammonia decomposition

  摘要 使用热解吸光谱、同位素交换热解吸和稳态分解测量研究了 Pt(111) 和阶梯状 Pt(S)-6(111) × (111) 表面上的氨吸附。同位素交换实验表明，分子氨在 400 K 以下的 Pt(111) 和 Pt(S)-6(111) × (111) 表面均无解离吸附。也就是说，氨吸附不受 ( 111) 低于 400 K 的类型台阶位点。在 90 K 处吸附后观察到三个不同的解吸峰。在 100 K 处的窄峰中解吸多层固体氨。分子氨的弱化学吸附高覆盖-低温形式在 150 K 处解吸具有一级动力学和 36 ± 3 kj mol (8.6 ± 0.6 kcal mol) 的解吸热。分子氨的化学吸附低覆盖-高温形式在 170 至 450 K 温度范围内以宽峰解吸。Pt(111) 表面在 400 K 以上发生稳态氨分解，表明在升高的温度下确实会发生解离吸附。