IB Chemistry — Structure 1 · 鼎睿学苑

Models of the Particulate Nature of Matter物质粒子性模型

From states of matter to electron configurations, from the mole concept to ideal gases. This unit builds the foundational models that underpin all of chemistry.从物质三态到电子构型(electron configuration),从摩尔(mole)概念到理想气体(ideal gas)。本单元搭建起支撑整门化学的基础模型。

SL: 17 hrs · HL: 21 hrsSL: 17 学时 · HL: 21 学时 5 Sub-topics5 个子主题 HL adds 1.2.3, 1.3.6, 1.3.7HL 加考 1.2.3、1.3.6、1.3.7

Introduction to the Particulate Nature of Matter物质粒子性导论

All matter is composed of particles. The three classifications of matter — elements, compounds, and mixtures — describe how those particles are organized and bonded. Understanding this hierarchy is the starting point for everything else in chemistry.一切物质都由粒子构成。物质的三种分类——元素(element)、化合物(compound)、混合物(mixture)——描述了这些粒子的组合方式与成键关系。理清这一层次结构是后续所有化学内容的起点。

Elements, Compounds, and Mixtures Elements cannot be chemically broken down into simpler substances. They consist of one type of atom. Compounds consist of atoms of different elements chemically bonded in a fixed ratio. Their properties differ from their constituent elements. Mixtures contain more than one element or compound in no fixed ratio, not chemically bonded — they can be separated by physical methods like filtration, distillation, evaporation, recrystallization, and chromatography.
元素、化合物与混合物 元素(element无法通过化学方法分解为更简单的物质,由同一种原子组成。 化合物(compound由不同元素的原子按固定比例化学键合而成,其性质与组成它的元素不同。 混合物(mixture含有一种以上的元素或化合物,比例不固定,组分之间没有化学键合——可通过过滤、蒸馏、蒸发、重结晶、色谱等物理方法(filtration / distillation / evaporation / recrystallization / chromatography)分离。
Homogeneous vs. Heterogeneous Mixtures A homogeneous mixture has uniform composition throughout (e.g., salt water, air). A heterogeneous mixture has visibly different components or phases (e.g., sand and water, oil and vinegar). The distinction matters when choosing separation techniques.
均相混合物与非均相混合物 均相(homogeneous混合物各处组成均匀(如盐水、空气);非均相(heterogeneous混合物可见地由不同组分或相组成(如沙与水、油与醋)。选择分离方法时这一区分至关重要。

Kinetic Molecular Theory and States of Matter分子运动论与物质三态

The kinetic molecular theory models matter as particles in constant motion. The three states — solid, liquid, and gas — differ in the arrangement, spacing, and motion of their particles. Solids have fixed positions with vibrational motion. Liquids have particles close together but able to slide past each other. Gases have widely spaced particles moving rapidly in all directions.分子运动论(kinetic molecular theory把物质看作不停运动的粒子集合。固、液、气三态在粒子排列、间距和运动方式上各不相同:固体粒子位置固定,仅作振动;液体粒子彼此靠近,但可相互滑动;气体粒子间距很大,向各方向高速运动。

Changes of State Melting (solid to liquid), freezing (liquid to solid), vaporization (liquid to gas — includes evaporation and boiling), condensation (gas to liquid), sublimation (solid to gas), and deposition (gas to solid). Each involves energy transfer: breaking intermolecular forces requires energy (endothermic), forming them releases energy (exothermic).
物态变化 熔化(melting,固→液)、凝固(freezing,液→固)、汽化(vaporization,液→气,包括蒸发与沸腾)、凝结(condensation,气→液)、升华(sublimation,固→气)、凝华(deposition,气→固)。每一种都涉及能量传递:克服分子间作用力(intermolecular force)需要吸热(endothermic),形成分子间作用力则放热(exothermic)。
State Symbols in Equations Always include state symbols: (s) solid, (l) liquid, (g) gas, (aq) aqueous (dissolved in water). These are required in IB Chemistry equations and carry marks in exams.
化学方程中的状态符号 化学方程中必须写出状态符号(state symbols):(s) 固态、(l) 液态、(g) 气态、(aq) 水溶液(溶于水)。IB Chemistry 方程式题强制要求,缺失会被扣分。

Temperature and Kinetic Energy温度与动能

Temperature in Kelvin (K) is a measure of the average kinetic energy ($E_k$) of particles. The kelvin has the same increment size as the Celsius degree. Converting between them:开尔文(K)温标度量的是粒子的平均动能($E_k$)。开尔文与摄氏度的刻度大小相同。两者换算:

Celsius ↔ Kelvin Conversion摄氏度与开尔文的换算
$$T(K) = T(°C) + 273$$

At 0 K (absolute zero), particles have minimum kinetic energy. During a change of state, temperature remains constant even though heat is being added or removed — the energy goes into breaking or forming intermolecular forces.

在 0 K(绝对零度,absolute zero)时粒子的动能最小。物态变化(phase change)过程中,即使持续吸热或放热,温度也保持不变——能量全部用于克服或形成分子间作用力。

During the melting of ice at 0 degrees C, which statement is correct?冰在 0 °C 熔化过程中,下列说法正确的是?
The kinetic energy of particles increases粒子的动能增加
The temperature rises steadily温度持续升高
Energy is used to overcome intermolecular forces能量用于克服分子间作用力
The particles stop moving粒子停止运动
Correct! During a phase change, added energy goes into overcoming intermolecular forces rather than increasing kinetic energy. The temperature stays constant until the phase change is complete.正确!物态变化期间,吸收的能量用于克服分子间作用力,而非增加动能。直到相变完成,温度始终保持不变。
During melting, the temperature remains constant. The added energy overcomes intermolecular forces rather than increasing particle speed. Answer: (C).熔化过程中温度保持不变。吸收的能量克服分子间作用力,而不是加快粒子运动。答案:(C)。
Going Deeper — Reading a Heating Curve When a solid is heated at a steady rate, a graph of temperature against time shows sloping sections separated by two flat plateaus. On a sloping section a single state is warming and the average kinetic energy of the particles rises. The first plateau marks the melting point and the second marks the boiling point. During each plateau the temperature is constant because the absorbed energy is used to overcome intermolecular forces — potential energy rises while average kinetic energy stays fixed. The boiling plateau is longer than the melting plateau because vaporisation must separate the particles completely, which requires far more energy than merely loosening the lattice during melting.
深入理解 — 读懂加热曲线 以恒定速率对固体加热时,温度—时间图(heating curve)由若干斜线段与两段水平平台组成。斜线段表示单一物态在升温、粒子平均动能上升。第一段平台对应熔点,第二段平台对应沸点。平台期温度不变,因为吸收的能量全部用于克服分子间作用力——势能升高而平均动能保持不变。沸腾平台比熔化平台更长,因为汽化必须使粒子彻底分离,所需能量远大于熔化时仅仅松动晶格。
Worked Example — Temperature Conversion and Kinetic Energy例题 — 温度换算与动能

Liquid nitrogen boils at $-196\;°$C. (a) Convert this temperature to kelvin. (b) A separate nitrogen sample is warmed from 77 K to 154 K. By what factor does the average kinetic energy of its particles change?

液氮在 $-196\;°$C 沸腾。(a) 将该温度换算为开尔文。(b) 另取一份氮气从 77 K 加热到 154 K,其粒子平均动能变为原来的几倍?

Part (a) — Celsius to kelvin
$$T = -196 + 273 = 77\;\text{K}$$
Absolute zero is the fixed reference point of the kelvin scale, so we simply add 273 to the Celsius value.
(a) — 摄氏转开尔文
$$T = -196 + 273 = 77\;\text{K}$$
绝对零度是开尔文标度的固定参考点,因此只需在摄氏数值上加 273。
Part (b) — Kinetic energy scales with absolute temperature
$$\bar{E}_k = \tfrac{3}{2}k_B T \implies \bar{E}_k \propto T$$
Average kinetic energy is directly proportional to the temperature in kelvin, so doubling $T$ from 77 K to 154 K doubles the average kinetic energy. This proportionality only holds in kelvin — taking the ratio in Celsius would be meaningless because the Celsius zero is arbitrary.
(b) — 动能与绝对温度成正比
$$\bar{E}_k = \tfrac{3}{2}k_B T \implies \bar{E}_k \propto T$$
平均动能与开尔文温度成正比,$T$ 由 77 K 翻倍到 154 K,平均动能也随之翻倍。该比例关系只在开尔文标度下成立——用摄氏度取比值毫无意义,因为摄氏零点是人为设定的。
Worked Example — Designing a Separation Scheme例题 — 设计分离方案

A solid mixture contains sand (insoluble in water), sodium chloride (soluble), and iodine (sublimes on gentle warming). Describe, in order, how to obtain a pure sample of each component.

某固体混合物含沙子(不溶于水)、氯化钠(可溶)与碘(微热即升华)。按顺序说明如何分别得到每种纯组分。

Step 1 — Remove iodine by sublimation
Warm the mixture gently. Iodine sublimes directly from solid to vapour and re-deposits on a cold surface held above the dish, leaving sand and salt behind.
第 1 步 — 升华除去碘
轻微加热混合物,碘由固态直接升华为蒸气,在上方冷表面重新凝华收集,留下沙与盐。
Step 2 — Dissolve and filter
Add water and stir: the salt dissolves but the sand does not. Filter the mixture — sand is collected as the residue while the salt solution passes through as the filtrate.
第 2 步 — 溶解并过滤
加水搅拌:盐溶解、沙不溶。过滤混合物——沙作为残渣收集,盐溶液作为滤液通过。
Step 3 — Evaporate to recover the salt
Evaporate the filtrate to crystallise the sodium chloride. Every step exploits a different physical property and no chemical bonds are broken — confirming the sample is a mixture, not a compound.
第 3 步 — 蒸发回收盐
蒸发滤液使氯化钠结晶析出。每一步都利用不同的物理性质,且没有破坏任何化学键——这正说明样品是混合物而非化合物。
Which of the following is best described as a homogeneous mixture?下列哪一项最适合描述为均相混合物?
Sand and water沙与水
Oil-and-vinegar salad dressing油醋沙拉汁
Granite rock花岗岩
Stainless steel不锈钢
Correct! Stainless steel is an alloy — a solid solution with uniform composition throughout, so it is homogeneous. The other three all show visibly distinct phases or grains.正确!不锈钢是合金——组成处处均匀的固溶体,属于均相混合物。其余三者都能看到明显不同的相或颗粒。
A homogeneous mixture has uniform composition with no visible boundaries between components. Only the alloy (stainless steel) qualifies. Answer: (D).均相混合物组成均匀,各组分间无可见界面。只有合金(不锈钢)符合。答案:(D)。

The Nuclear Atom核式原子模型

Atoms consist of a positively charged, dense nucleus containing protons and neutrons (collectively called nucleons), surrounded by negatively charged electrons. The nuclear symbol $_Z^A X$ encodes the identity and composition of any atom or ion.原子由带正电的致密原子核(含质子与中子,二者统称核子)和围绕其外、带负电的电子组成。核符号(nuclear symbol)$_Z^A X$ 编码了任意原子或离子的身份与组成。

Nuclear Symbol核符号
$$_Z^A X$$

$Z$ = atomic number (protons), $A$ = mass number (protons + neutrons). Neutrons = $A - Z$. For neutral atoms, electrons = protons = $Z$.

$Z$ = 原子序数(atomic number,质子数),$A$ = 质量数(mass number,质子数+中子数)。中子数 = $A - Z$。中性原子的电子数等于质子数,即 $Z$。

Subatomic Particles亚原子粒子
ParticleRelative MassRelative ChargeLocation
Proton1+1Nucleus
Neutron10Nucleus
Electron~1/1840 (negligible)-1Electron shells
粒子相对质量相对电荷位置
质子 (proton)1+1原子核
中子 (neutron)10原子核
电子 (electron)约 1/1840(可忽略)-1电子壳层

Isotopes同位素

Isotopes are atoms of the same element (same number of protons) with different numbers of neutrons. They have identical chemical properties but different physical properties (mass, density, rate of diffusion). The relative atomic mass ($A_r$) of an element is a weighted average of its isotopic masses based on their natural abundances.同位素(isotope是同一元素(质子数相同)但中子数不同的原子。它们化学性质相同,但物理性质(质量、密度、扩散速率)有差异。元素的相对原子质量(relative atomic mass,$A_r$)是按自然丰度对各同位素质量取的加权平均值。

Worked Example — Relative Atomic Mass from Isotopic Data例题 — 由同位素数据求相对原子质量

Chlorine has two isotopes: $^{35}$Cl (75.77%) and $^{37}$Cl (24.23%). Calculate the relative atomic mass.

氯有两种同位素:$^{35}$Cl(75.77%)与 $^{37}$Cl(24.23%)。求其相对原子质量。

Weighted average
$$A_r = \frac{(35 \times 75.77) + (37 \times 24.23)}{100}$$
$$A_r = \frac{2651.95 + 896.51}{100} = \frac{3548.46}{100} = 35.48$$
This is why chlorine's relative atomic mass is approximately 35.5, not a whole number.
加权平均
$$A_r = \frac{(35 \times 75.77) + (37 \times 24.23)}{100}$$
$$A_r = \frac{2651.95 + 896.51}{100} = \frac{3548.46}{100} = 35.48$$
这就是氯的相对原子质量约为 35.5(而非整数)的原因。
Relative Isotopic Mass vs. Relative Atomic Mass These two terms are easy to conflate but mean different things. Relative isotopic mass is the mass of one specific isotope compared to $^{12}$C — e.g. $^{35}$Cl has a relative isotopic mass very close to 35 (a near-whole number, since it's dominated by whole numbers of protons and neutrons). Relative atomic mass ($A_r$) is the weighted average across all naturally occurring isotopes — chlorine's is 35.5, not close to any single isotope, precisely because it blends $^{35}$Cl and $^{37}$Cl in their natural proportions.
相对同位素质量 vs. 相对原子质量 这两个术语容易混淆,但含义不同。相对同位素质量(relative isotopic mass是某一种具体同位素相对于 $^{12}$C 的质量——例如 $^{35}$Cl 的相对同位素质量非常接近 35(近乎整数,因为它主要由整数个质子和中子决定)。相对原子质量($A_r$)则是所有天然同位素的加权平均值——氯的 $A_r$ 为 35.5,并不接近任何单一同位素的质量,正是因为它按天然比例混合了 $^{35}$Cl 与 $^{37}$Cl。
HL Only — Mass Spectrometry (1.2.3) Mass spectra show peaks corresponding to each isotope. The $x$-axis shows mass-to-charge ratio ($m/z$), and the $y$-axis shows relative abundance. You can read off isotopic masses and their abundances directly from the spectrum and calculate $A_r$ from the data.
仅 HL — 质谱法(1.2.3) 质谱图(mass spectrum)上每个同位素对应一个峰。横轴是质荷比(mass-to-charge ratio,$m/z$),纵轴是相对丰度(relative abundance)。可直接从谱图读出各同位素的质量与丰度,并据此计算 $A_r$。
Worked Example — Relative Atomic Mass from a Mass Spectrum (HL)例题 — 由质谱图求相对原子质量(HL)

A mass spectrum of gallium shows two peaks: $m/z = 69$ with relative abundance 60.1%, and $m/z = 71$ with relative abundance 39.9%. Calculate the relative atomic mass of gallium.

镓的质谱图显示两个峰:$m/z = 69$(相对丰度 60.1%)与 $m/z = 71$(相对丰度 39.9%)。求镓的相对原子质量。

Step 1 — Read peak positions and heights directly from the spectrum
The $x$-axis position of each peak is the isotopic mass; the peak height (or area) is the relative abundance. No other data is needed.
Step 2 — Weighted average
$$A_r = \frac{(69 \times 60.1) + (71 \times 39.9)}{100}$$
$$A_r = \frac{4146.9 + 2832.9}{100} = \frac{6979.8}{100} = 69.80$$
Step 3 — Sanity check
The answer (69.80) lies between the two isotopic masses (69 and 71), closer to 69 — which makes sense since the lighter isotope is the more abundant one. Gallium's data-booklet $A_r$ is 69.72, matching closely.
第 1 步 — 直接从谱图读出峰的位置与高度
每个峰的横轴位置就是该同位素的质量;峰的高度(或面积)就是相对丰度。不需要其他数据。
第 2 步 — 加权平均
$$A_r = \frac{(69 \times 60.1) + (71 \times 39.9)}{100}$$
$$A_r = \frac{4146.9 + 2832.9}{100} = \frac{6979.8}{100} = 69.80$$
第 3 步 — 合理性检验
结果(69.80)落在两个同位素质量(69 与 71)之间,且更接近 69——这是合理的,因为较轻的同位素丰度更高。镓的数据手册 $A_r$ 值为 69.72,与之高度吻合。
An atom of $_{26}^{56}$Fe$^{3+}$ contains:$_{26}^{56}$Fe$^{3+}$ 含有:
26 protons, 30 neutrons, 26 electrons26 个质子、30 个中子、26 个电子
26 protons, 30 neutrons, 23 electrons26 个质子、30 个中子、23 个电子
26 protons, 56 neutrons, 23 electrons26 个质子、56 个中子、23 个电子
56 protons, 26 neutrons, 53 electrons56 个质子、26 个中子、53 个电子
Correct! Protons = $Z$ = 26. Neutrons = $A - Z$ = 56 - 26 = 30. The 3+ charge means 3 electrons were lost: 26 - 3 = 23 electrons.正确!质子数 = $Z$ = 26;中子数 = $A - Z$ = 56 - 26 = 30;3+ 电荷意味着失去 3 个电子,故电子数 = 26 - 3 = 23。
$Z$ = 26 protons, neutrons = 56 - 26 = 30, and the 3+ charge means 3 fewer electrons than protons: 26 - 3 = 23. Answer: (B).$Z$ = 26 个质子;中子 = 56 - 26 = 30;3+ 表示电子比质子少 3 个:26 - 3 = 23。答案:(B)。

Electron Configurations电子构型

Emission Spectra and Energy Levels发射光谱与能级

When atoms absorb energy, electrons are excited to higher energy levels. When they fall back down, they emit photons of specific energies, producing a line emission spectrum. The hydrogen emission spectrum provides direct evidence that electrons exist in discrete (quantized) energy levels that converge at higher energies.当原子吸收能量时,电子被激发到更高的能级;当它们跃迁回较低能级时,发射出特定能量的光子,形成线状发射光谱(line emission spectrum。氢原子发射光谱直接证明:电子处于离散(量子化)能级,且能级在高能端逐渐汇聚。

Continuous vs. Line Spectra A continuous spectrum contains all wavelengths (like white light through a prism). A line spectrum contains only specific wavelengths, corresponding to specific energy transitions within atoms. Each element has a unique line spectrum — a chemical fingerprint.
连续光谱与线状光谱 连续光谱(continuous spectrum包含所有波长(如白光经棱镜色散);线状光谱(line spectrum只含特定波长,对应原子内特定的能级跃迁。每种元素的线状光谱独一无二——堪称化学指纹。

Main Energy Levels and Sublevels主能级与亚层

The main energy level is given by the integer $n$ (1, 2, 3...) and can hold a maximum of $2n^2$ electrons. Within each main level, electrons occupy sublevels: s, p, d, and f, each with successively higher energy.主能级由整数 $n$(1、2、3……)标记,最多容纳 $2n^2$ 个电子。在每个主能级内,电子分布于亚层(subshell):s、p、d、f,能量依次升高。

Sublevel Summary亚层总览
SublevelOrbitalsMax ElectronsShape
s12Spherical
p36Dumbbell (3 orientations)
d510Complex (various)
f714Complex (various)
亚层轨道数最大电子数形状
s12球形
p36哑铃形(3 种取向)
d510复杂(多种形状)
f714复杂(多种形状)
HL Only — Orbital Shapes and Degeneracy An orbital is a region of space where there is a high probability of finding an electron — not a fixed orbit. All three $p$ orbitals in a sublevel ($p_x$, $p_y$, $p_z$) have identical dumbbell shapes but point along different axes; all five $d$ orbitals likewise have the same energy within a free atom. Orbitals of equal energy within the same sublevel are called degenerate — this is exactly why Hund's rule matters: electrons spread across degenerate orbitals singly before any pairing occurs, since pairing in the same orbital costs extra energy from electron–electron repulsion.
仅 HL — 轨道形状与简并 轨道(orbital是电子出现概率较高的空间区域——而不是一条固定的轨迹。同一亚层的三个 $p$ 轨道($p_x$、$p_y$、$p_z$)形状完全相同,只是指向不同的坐标轴;同理,五个 $d$ 轨道在自由原子中能量也相同。同一亚层中能量相等的轨道称为简并(degenerate轨道——这正是洪德规则起作用的原因:电子会先单独占据简并轨道,之后才会配对,因为在同一轨道中配对会因电子间排斥而多耗能量。

Electron Configuration Rules电子排布规则

Three principles govern how electrons fill orbitals:三条原则规定了电子如何填充轨道(orbital):

Filling Rules Aufbau principle: Electrons fill the lowest energy orbitals first (1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p...). Hund's rule: Electrons occupy degenerate orbitals singly before pairing up, all with the same spin. Pauli exclusion principle: Each orbital holds a maximum of 2 electrons, which must have opposite spins.
填充规则 构造原理(Aufbau principle):电子优先填入能量最低的轨道(1s、2s、2p、3s、3p、4s、3d、4p……)。 洪德规则(Hund's rule):电子先单占简并轨道、自旋方向相同,最后才两两配对。 泡利不相容原理(Pauli exclusion principle):每个轨道最多容纳 2 个电子,且二者自旋必须相反。
Exceptions: Chromium and Copper Cr (Z=24): expected [Ar] 3d$^4$ 4s$^2$, actual [Ar] 3d$^5$ 4s$^1$. Cu (Z=29): expected [Ar] 3d$^9$ 4s$^2$, actual [Ar] 3d$^{10}$ 4s$^1$. A half-filled or fully filled d-sublevel provides extra stability. You must know these two exceptions.
两个例外:铬与铜 Cr(Z=24):按规则应为 [Ar] 3d$^4$ 4s$^2$,实际为 [Ar] 3d$^5$ 4s$^1$。Cu(Z=29):按规则应为 [Ar] 3d$^9$ 4s$^2$,实际为 [Ar] 3d$^{10}$ 4s$^1$。半充满或全充满的 d 亚层更稳定。这两个例外必须记住。
Worked Example — Electron Configuration例题 — 电子构型

Write the full and condensed electron configurations for Fe (Z=26) and Fe$^{2+}$.

写出 Fe(Z=26)与 Fe$^{2+}$ 的完整电子构型与缩写电子构型。

Fe (26 electrons)
Full: 1s$^2$ 2s$^2$ 2p$^6$ 3s$^2$ 3p$^6$ 4s$^2$ 3d$^6$
Condensed: [Ar] 4s$^2$ 3d$^6$
Fe(26 个电子)
完整式:1s$^2$ 2s$^2$ 2p$^6$ 3s$^2$ 3p$^6$ 4s$^2$ 3d$^6$
缩写式:[Ar] 4s$^2$ 3d$^6$
Fe$^{2+}$ (24 electrons)
When transition metals form ions, electrons are removed from the 4s sublevel first (not 3d).
Fe$^{2+}$: [Ar] 3d$^6$
The 4s electrons are lost before the 3d electrons because in an ion, 3d is lower in energy than 4s.
Fe$^{2+}$(24 个电子)
过渡金属形成阳离子时,电子先从 4s 亚层失去,而不是 3d。
Fe$^{2+}$:[Ar] 3d$^6$
先失 4s 后失 3d 的原因是:在离子中 3d 的能量低于 4s。
HL Only — Ionization Energy from Spectra (1.3.6–1.3.7) The convergence limit of spectral lines corresponds to ionization. The first ionization energy can be calculated from the frequency of the convergence limit: $IE = hf$ or $IE = hc/\lambda$. Successive IE data reveal the electron configuration — large jumps between successive IEs indicate electrons being removed from a different shell. IE trends and discontinuities across a period provide evidence for the existence of sublevels.
仅 HL — 从光谱求电离能(1.3.6—1.3.7) 光谱线的汇聚极限对应电离过程。第一电离能(ionization energy)可由汇聚极限的频率求得:$IE = hf$ 或 $IE = hc/\lambda$。逐级电离能数据可揭示电子构型——相邻两级电离能突然变大,说明电子是从不同的电子壳层被移除的。同一周期内电离能的趋势与突变也为亚层的存在提供证据。
Worked Example — Ionization Energy from Convergence Frequency (HL)例题 — 由汇聚频率求电离能(HL)

The convergence limit of the Lyman series in hydrogen's emission spectrum occurs at a frequency of $3.29 \times 10^{15}\;\text{Hz}$. Calculate the first ionization energy of hydrogen in kJ mol$^{-1}$ ($h = 6.63\times10^{-34}\;\text{J s}$, $N_A = 6.022\times10^{23}\;\text{mol}^{-1}$).

氢原子发射光谱中莱曼系(Lyman series)的汇聚频率为 $3.29 \times 10^{15}\;\text{Hz}$。求氢的第一电离能(单位 kJ mol$^{-1}$,取 $h = 6.63\times10^{-34}\;\text{J s}$,$N_A = 6.022\times10^{23}\;\text{mol}^{-1}$)。

Step 1 — Energy of one atom's ionization
$$E = hf = (6.63\times10^{-34})(3.29\times10^{15}) = 2.18\times10^{-18}\;\text{J}$$
Step 2 — Scale up to one mole
$$E_\text{molar} = (2.18\times10^{-18})(6.022\times10^{23}) = 1.31\times10^{6}\;\text{J mol}^{-1} = 1310\;\text{kJ mol}^{-1}$$
This matches the data-booklet first ionization energy of hydrogen (1312 kJ mol$^{-1}$) closely.
第 1 步 — 单个原子电离所需能量
$$E = hf = (6.63\times10^{-34})(3.29\times10^{15}) = 2.18\times10^{-18}\;\text{J}$$
第 2 步 — 换算到每摩尔
$$E_\text{molar} = (2.18\times10^{-18})(6.022\times10^{23}) = 1.31\times10^{6}\;\text{J mol}^{-1} = 1310\;\text{kJ mol}^{-1}$$
与数据手册中氢的第一电离能(1312 kJ mol$^{-1}$)高度吻合。
Going Deeper — Reading a Successive Ionization Energy Graph A graph of $\log(IE)$ against "electron removed" for a given element shows several roughly flat steps separated by sharp jumps. Each flat step corresponds to electrons being removed from within the same main energy level (or sublevel); a sharp jump means the next electron comes from a shell much closer to the nucleus, which is far harder to remove. Counting the number of electrons in each step before a jump directly reveals the electron arrangement into shells — e.g. a 2-8-1 pattern (steps of size 2, then 8, then 1 before running out of easy electrons) is exactly what you'd see for sodium, without ever citing its electron configuration by name.
深入理解 — 读懂逐级电离能图 对某元素画出 $\log(IE)$ 相对于"被移除的第几个电子"的图,会看到若干大致平坦的台阶,中间被陡峭的跳跃隔开。每一段平台对应的电子都来自同一主能级(或亚层);一次陡峭的跳跃说明下一个电子来自离核更近得多的壳层,因而难移除得多。数出每次跳跃前那一段台阶包含多少个电子,就能直接揭示电子按壳层的排布——例如 2-8-1 的模式(台阶大小依次为 2、然后 8、然后 1 个"容易移除"的电子后就用完了),正是钠会呈现的图像,甚至不需要直接说出它的电子构型。
Worked Example — Isoelectronic Ions例题 — 等电子离子

Write the electron configuration shared by O$^{2-}$, F$^-$, Na$^+$, and Mg$^{2+}$, and explain why they are described as isoelectronic.

写出 O$^{2-}$、F$^-$、Na$^+$ 与 Mg$^{2+}$ 共有的电子构型,并说明为什么它们被称为等电子体。

Step 1 — Count electrons for each species
O$^{2-}$: 8 + 2 = 10. F$^-$: 9 + 1 = 10. Na$^+$: 11 - 1 = 10. Mg$^{2+}$: 12 - 2 = 10. All four species have exactly 10 electrons, despite having four different atomic numbers.
第 1 步 — 分别数出每种粒子的电子数
O$^{2-}$:8 + 2 = 10。F$^-$:9 + 1 = 10。Na$^+$:11 - 1 = 10。Mg$^{2+}$:12 - 2 = 10。这四种粒子的原子序数各不相同,但电子数都恰好是 10。
Step 2 — Write the shared configuration
$$1s^2\,2s^2\,2p^6 \quad (\text{= [Ne] configuration})$$
第 2 步 — 写出共有的构型
$$1s^2\,2s^2\,2p^6 \quad (\text{即 [Ne] 构型})$$
Step 3 — Why "isoelectronic" matters
Species with identical electron configurations ("iso" = same, "electronic" = electron arrangement) tend to share some physical properties — but not all, since nuclear charge still differs. Ionic radius is the clearest example: across this isoelectronic series, radius shrinks from O$^{2-}$ to Mg$^{2+}$ because the same 10 electrons are pulled in by an increasingly large nuclear charge (8+, 9+, 11+, 12+).
第 3 步 — "等电子"为何重要
电子构型相同("iso" 意为相同,"electronic" 指电子排布)的粒子往往具有一些相似的物理性质——但并非全部相同,因为核电荷仍不相同。离子半径就是最清楚的例子:在这一等电子系列中,半径从 O$^{2-}$ 到 Mg$^{2+}$ 逐渐缩小,因为同样的 10 个电子被越来越大的核电荷(8+、9+、11+、12+)吸引。
What is the electron configuration of Cu (Z=29)?Cu(Z=29)的电子构型是?
[Ar] 3d$^9$ 4s$^2$
[Ar] 3d$^8$ 4s$^2$ 4p$^1$
[Ar] 3d$^{10}$ 4s$^2$
[Ar] 3d$^{10}$ 4s$^1$
Correct! Copper is one of two required exceptions. A fully filled 3d$^{10}$ sublevel is more stable, so one 4s electron is promoted: [Ar] 3d$^{10}$ 4s$^1$.正确!铜是必考的两个例外之一。3d$^{10}$ 全充满更稳定,因此一个 4s 电子被"提"到 3d:[Ar] 3d$^{10}$ 4s$^1$。
Cu is an exception: [Ar] 3d$^{10}$ 4s$^1$, not the expected [Ar] 3d$^9$ 4s$^2$. Answer: (D).Cu 是例外:实际为 [Ar] 3d$^{10}$ 4s$^1$,不是 [Ar] 3d$^9$ 4s$^2$。答案:(D)。

Counting Particles by Mass: The Mole用质量数粒子:摩尔

The mole (mol) is the SI unit of amount of substance. One mole contains exactly the number of elementary entities given by the Avogadro constant ($N_A = 6.022 \times 10^{23}$ mol$^{-1}$). An elementary entity can be an atom, molecule, ion, electron, or any specified particle.摩尔(mole,mol)是 SI 单位制中物质的量的基本单位。1 mol 含有的基本粒子数由阿伏伽德罗常数(Avogadro's constant)给出:$N_A = 6.022 \times 10^{23}$ mol$^{-1}$。基本粒子可以是原子、分子、离子、电子或任何指明的粒子。

The Mole Triangle摩尔三角
$$n = \frac{m}{M} \qquad n = \frac{N}{N_A} \qquad n = C \times V$$

$n$ = amount (mol), $m$ = mass (g), $M$ = molar mass (g mol$^{-1}$), $N$ = number of particles, $N_A$ = Avogadro constant, $C$ = concentration (mol dm$^{-3}$), $V$ = volume (dm$^3$).

$n$ = 物质的量(mol);$m$ = 质量(g);$M$ = 摩尔质量(molar mass,g mol$^{-1}$);$N$ = 粒子数;$N_A$ = 阿伏伽德罗常数;$C$ = 浓度(concentration,mol dm$^{-3}$);$V$ = 体积(dm$^3$)。

Relative Masses相对质量

Masses of atoms are compared on a scale relative to $^{12}$C. The relative atomic mass ($A_r$) and relative formula mass ($M_r$) are dimensionless (no units). The molar mass ($M$) has units g mol$^{-1}$ and is numerically equal to $M_r$.原子质量以 $^{12}$C 为基准进行比较。相对原子质量(relative atomic mass,$A_r$)相对式量(relative formula mass,$M_r$)是无量纲量。摩尔质量(molar mass,$M$)的单位是 g mol$^{-1}$,数值上等于 $M_r$。

Empirical and Molecular Formulas实验式与分子式

The empirical formula gives the simplest whole-number ratio of atoms. The molecular formula gives the actual number of atoms in a molecule. To find the molecular formula, divide the molar mass by the empirical formula mass to get a multiplier.实验式(empirical formula给出原子数的最简整数比;分子式(molecular formula给出分子中各原子的真实个数。用摩尔质量除以实验式式量,即可得到倍数,进而得到分子式。

Worked Example — Empirical Formula from Percentage Composition例题 — 由质量百分比求实验式

A compound contains 40.0% C, 6.7% H, and 53.3% O by mass. Its molar mass is 180 g mol$^{-1}$. Find the empirical and molecular formulas.

某化合物按质量计含 40.0% C、6.7% H、53.3% O,其摩尔质量为 180 g mol$^{-1}$。求其实验式与分子式。

Step 1 — Assume 100 g, convert to moles
$$n_C = \frac{40.0}{12.01} = 3.33 \quad n_H = \frac{6.7}{1.01} = 6.63 \quad n_O = \frac{53.3}{16.00} = 3.33$$
第 1 步 — 设总质量为 100 g,换算为摩尔数
$$n_C = \frac{40.0}{12.01} = 3.33 \quad n_H = \frac{6.7}{1.01} = 6.63 \quad n_O = \frac{53.3}{16.00} = 3.33$$
Step 2 — Divide by smallest
$$C: \frac{3.33}{3.33} = 1 \quad H: \frac{6.63}{3.33} = 2 \quad O: \frac{3.33}{3.33} = 1$$
Empirical formula: CH$_2$O. Empirical formula mass = 12 + 2 + 16 = 30.
第 2 步 — 全部除以最小者
$$C: \frac{3.33}{3.33} = 1 \quad H: \frac{6.63}{3.33} = 2 \quad O: \frac{3.33}{3.33} = 1$$
实验式:CH$_2$O。实验式式量 = 12 + 2 + 16 = 30。
Step 3 — Find molecular formula
$$\text{Multiplier} = \frac{180}{30} = 6$$
Molecular formula: C$_6$H$_{12}$O$_6$ (glucose).
第 3 步 — 求分子式
$$\text{倍数} = \frac{180}{30} = 6$$
分子式:C$_6$H$_{12}$O$_6$(葡萄糖)。
Worked Example — Water of Crystallization例题 — 结晶水

A hydrated salt has the formula MgSO$_4\cdot x$H$_2$O. Heating 2.46 g of the hydrate to constant mass leaves 1.20 g of anhydrous MgSO$_4$ ($M = 120.4$ g mol$^{-1}$). Find $x$.

某水合盐的化学式为 MgSO$_4\cdot x$H$_2$O。将 2.46 g 该水合物加热至质量恒定,剩下 1.20 g 无水 MgSO$_4$($M = 120.4$ g mol$^{-1}$)。求 $x$。

Step 1 — Mass and moles of water lost
Mass of water driven off: $2.46 - 1.20 = 1.26$ g.
$$n(\text{H}_2\text{O}) = \frac{1.26}{18.02} = 0.0699\;\text{mol}$$
第 1 步 — 失去的水的质量与物质的量
失去的水的质量:$2.46 - 1.20 = 1.26$ g。
$$n(\text{H}_2\text{O}) = \frac{1.26}{18.02} = 0.0699\;\text{mol}$$
Step 2 — Moles of anhydrous salt
$$n(\text{MgSO}_4) = \frac{1.20}{120.4} = 0.00997\;\text{mol}$$
第 2 步 — 无水盐的物质的量
$$n(\text{MgSO}_4) = \frac{1.20}{120.4} = 0.00997\;\text{mol}$$
Step 3 — Mole ratio gives x
$$x = \frac{n(\text{H}_2\text{O})}{n(\text{MgSO}_4)} = \frac{0.0699}{0.00997} \approx 7$$
So the formula is MgSO$_4\cdot 7$H$_2$O (Epsom salt). This is the same empirical-formula logic as before, just with "moles of water" and "moles of salt" playing the role of two elements in a ratio.
第 3 步 — 摩尔比求 x
$$x = \frac{n(\text{H}_2\text{O})}{n(\text{MgSO}_4)} = \frac{0.0699}{0.00997} \approx 7$$
因此化学式为 MgSO$_4\cdot 7$H$_2$O(泻盐)。这与前面求实验式的逻辑完全一样,只是这里"水的物质的量"与"盐的物质的量"扮演了比例中两种元素的角色。
Worked Example — Percentage Composition by Mass (the Reverse Direction)例题 — 由化学式求质量百分比(反方向计算)

Calculate the percentage by mass of nitrogen in ammonium nitrate, NH$_4$NO$_3$ ($M = 80.06$ g mol$^{-1}$).

求硝酸铵 NH$_4$NO$_3$($M = 80.06$ g mol$^{-1}$)中氮的质量百分比。

Step 1 — Identify how many N atoms are in the formula
NH$_4$NO$_3$ contains two nitrogen atoms per formula unit — one in the ammonium ion, one in the nitrate ion. This is the step most often missed: counting only one N because the formula "looks like" it has one obvious nitrogen.
第 1 步 — 确定化学式中氮原子的个数
NH$_4$NO$_3$ 每个式量单元中含两个氮原子——铵根离子中一个,硝酸根离子中一个。这一步最容易被漏掉:因为化学式"看起来"只有一个明显的氮,就误以为只有一个。
Step 2 — Total mass of nitrogen per mole of compound
$$m(\text{N}) = 2 \times 14.01 = 28.02\;\text{g}$$
第 2 步 — 每摩尔化合物中氮的总质量
$$m(\text{N}) = 2 \times 14.01 = 28.02\;\text{g}$$
Step 3 — Divide by the molar mass and convert to a percentage
$$\%\text{N} = \frac{28.02}{80.06} \times 100 = 35.0\%$$
Percentage composition and empirical formula are inverse problems: one goes from formula to percentages, the other from percentages to formula, but both rely on exactly the same molar-mass bookkeeping.
第 3 步 — 除以摩尔质量并换算为百分比
$$\%\text{N} = \frac{28.02}{80.06} \times 100 = 35.0\%$$
质量百分比与实验式是互逆的问题:一个从化学式求百分比,另一个从百分比求化学式,但两者依赖的都是完全相同的摩尔质量记账方法。

Concentration and Dilution浓度与稀释

Molar concentration is determined by the amount of solute and the volume of solution. Square brackets denote concentration: [NaOH] means the molar concentration of NaOH in mol dm$^{-3}$. You should also be able to convert between g dm$^{-3}$ and mol dm$^{-3}$.摩尔浓度由溶质的物质的量与溶液体积决定。方括号代表浓度:[NaOH] 即 NaOH 的摩尔浓度(mol dm$^{-3}$)。你还应能在 g dm$^{-3}$ 与 mol dm$^{-3}$ 之间互换。

Worked Example — Dilution Calculation例题 — 稀释计算

25.0 cm$^3$ of 2.00 mol dm$^{-3}$ HCl is diluted to a final volume of 250 cm$^3$. What is the new concentration?

将 25.0 cm$^3$、2.00 mol dm$^{-3}$ 的 HCl 稀释至最终体积 250 cm$^3$。求新浓度。

Step 1 — Moles of solute don't change on dilution
$$n = C \times V = 2.00 \times \frac{25.0}{1000} = 0.0500\;\text{mol}$$
第 1 步 — 稀释不改变溶质的物质的量
$$n = C \times V = 2.00 \times \frac{25.0}{1000} = 0.0500\;\text{mol}$$
Step 2 — New concentration uses the same moles, new (larger) volume
$$C_2 = \frac{n}{V_2} = \frac{0.0500}{\frac{250}{1000}} = \frac{0.0500}{0.250} = 0.200\;\text{mol dm}^{-3}$$
第 2 步 — 新浓度用同样的物质的量、新的(更大的)体积
$$C_2 = \frac{n}{V_2} = \frac{0.0500}{\frac{250}{1000}} = \frac{0.0500}{0.250} = 0.200\;\text{mol dm}^{-3}$$
Shortcut
Equivalently, $C_1V_1 = C_2V_2$ (both sides equal the constant moles of solute): $(2.00)(25.0) = C_2(250) \Rightarrow C_2 = 0.200\;\text{mol dm}^{-3}$. The volume increased 10-fold (25.0 → 250), so the concentration dropped to exactly 1/10.
简便算法
等价地,$C_1V_1 = C_2V_2$(两边都等于不变的溶质物质的量):$(2.00)(25.0) = C_2(250) \Rightarrow C_2 = 0.200\;\text{mol dm}^{-3}$。体积扩大了 10 倍(25.0 → 250),所以浓度恰好降为原来的 1/10。

Avogadro's Law阿伏伽德罗定律

Equal volumes of all gases at the same temperature and pressure contain equal numbers of molecules. This means the mole ratio in a balanced equation directly gives the volume ratio for gaseous reactants and products.同温同压下,等体积的任何气体含有相同数目的分子(Avogadro's law)。因此,配平方程中的摩尔比就是气态反应物与产物的体积比。

Worked Example — Gas Volumes from a Balanced Equation例题 — 由配平方程求气体体积

Propane burns completely: C$_3$H$_8$(g) + 5O$_2$(g) → 3CO$_2$(g) + 4H$_2$O(g). At constant temperature and pressure, what volume of O$_2$ is needed to completely burn 3.00 dm$^3$ of propane, and what volume of CO$_2$ is produced?

丙烷完全燃烧:C$_3$H$_8$(g) + 5O$_2$(g) → 3CO$_2$(g) + 4H$_2$O(g)。在恒温恒压下,完全燃烧 3.00 dm$^3$ 丙烷需要多少体积的 O$_2$?生成多少体积的 CO$_2$?

Step 1 — By Avogadro's law, volume ratio = mole ratio
Directly from the balanced equation's coefficients: C$_3$H$_8$ : O$_2$ : CO$_2$ = 1 : 5 : 3.
第 1 步 — 由阿伏伽德罗定律,体积比 = 摩尔比
直接由配平方程的系数得:C$_3$H$_8$ : O$_2$ : CO$_2$ = 1 : 5 : 3。
Step 2 — Scale the ratio to the given volume
$$V(\text{O}_2) = 5 \times 3.00 = 15.0\;\text{dm}^3 \qquad V(\text{CO}_2) = 3 \times 3.00 = 9.00\;\text{dm}^3$$
No moles, mass, or molar volume are needed at all — because temperature and pressure are constant and equal for every gas in the reaction, the coefficients convert directly to volumes with no unit conversion.
第 2 步 — 按比例放大到给定体积
$$V(\text{O}_2) = 5 \times 3.00 = 15.0\;\text{dm}^3 \qquad V(\text{CO}_2) = 3 \times 3.00 = 9.00\;\text{dm}^3$$
完全不需要物质的量、质量或摩尔体积——因为反应中每种气体的温度和压强都相同且恒定,系数可以直接换算成体积,不需要任何单位换算。
How many molecules are in 0.50 mol of H$_2$O?0.50 mol H$_2$O 中有多少个分子?
$6.022 \times 10^{23}$
$3.011 \times 10^{23}$
$1.204 \times 10^{24}$
$9.033 \times 10^{23}$
Correct! $N = n \times N_A = 0.50 \times 6.022 \times 10^{23} = 3.011 \times 10^{23}$ molecules.正确!$N = n \times N_A = 0.50 \times 6.022 \times 10^{23} = 3.011 \times 10^{23}$ 个分子。
$N = n \times N_A = 0.50 \times 6.022 \times 10^{23} = 3.011 \times 10^{23}$. Answer: (B).$N = n \times N_A = 0.50 \times 6.022 \times 10^{23} = 3.011 \times 10^{23}$。答案:(B)。

Ideal Gases理想气体

An ideal gas is a theoretical model where particles have negligible volume and no intermolecular forces, and all collisions are elastic. Real gases approximate ideal behavior at high temperatures and low pressures (where particles are far apart and moving fast).理想气体(ideal gas是一个理论模型:粒子自身体积可忽略、粒子间无作用力,且所有碰撞均为弹性碰撞。真实气体在高温低压(粒子彼此距离远、运动快)时近似服从理想气体行为。

When Real Gases Deviate Real gases deviate from ideal behavior at low temperature (particles move slowly, intermolecular forces become significant) and high pressure (particles are close together, their volume is no longer negligible). Gases with stronger intermolecular forces (e.g., polar molecules, larger molecules) deviate more.
真实气体何时偏离理想行为 真实气体在低温(粒子运动慢,分子间作用力显著)与高压(粒子彼此靠近,自身体积不再可忽略)下偏离理想行为。分子间作用力越强(如极性分子、较大分子)偏离越显著。
Going Deeper — Where the Ideal Gas Assumptions Break Down Mathematically The van der Waals equation, $\left(P + \dfrac{an^2}{V^2}\right)(V - nb) = nRT$, patches the two ideal-gas assumptions directly. The term $\dfrac{an^2}{V^2}$ added to $P$ compensates for intermolecular attractions, which make the measured pressure slightly lower than an ideal gas would produce (attracted particles hit the walls a little less forcefully). The term $nb$ subtracted from $V$ compensates for the real, non-negligible volume the particles themselves occupy. Both correction terms shrink toward zero as $V$ becomes large (low pressure, particles far apart) and $T$ becomes high (fast-moving particles for which weak attractions barely matter) — exactly recovering $PV = nRT$ in the ideal limit.
拓展 — 理想气体假设在数学上如何被修正 范德华方程van der Waals equation)$\left(P + \dfrac{an^2}{V^2}\right)(V - nb) = nRT$ 直接修补了理想气体的两条假设。加到 $P$ 上的 $\dfrac{an^2}{V^2}$ 项补偿了分子间吸引力——吸引力会使实测压强略低于理想气体给出的值(相互吸引的粒子撞击器壁的力会稍弱)。从 $V$ 中减去的 $nb$ 项补偿了粒子自身不可忽略的真实体积。当 $V$ 变大(低压、粒子相距很远)且 $T$ 变高(粒子运动快,微弱的吸引力几乎无关紧要)时,这两个修正项都趋于零——恰好在理想极限下还原为 $PV = nRT$。

Molar Volume and the Ideal Gas Equation摩尔体积与理想气体方程

At STP (273.15 K, 100 kPa), the molar volume of an ideal gas is 22.7 dm$^3$ mol$^{-1}$ (given in the data booklet). The ideal gas equation relates all four state variables:在 STP(STP,273.15 K、100 kPa)下,理想气体的摩尔体积(molar volume)为 22.7 dm$^3$ mol$^{-1}$(数据手册中给出)。理想气体方程把四个状态变量联系起来:

Ideal Gas Equation理想气体方程
$$PV = nRT$$

$P$ = pressure (Pa), $V$ = volume (m$^3$), $n$ = moles (mol), $R$ = 8.314 J K$^{-1}$ mol$^{-1}$, $T$ = temperature (K). Use SI units throughout.

$P$ = 压强(Pa),$V$ = 体积(m$^3$),$n$ = 物质的量(mol),$R$ = 8.314 J K$^{-1}$ mol$^{-1}$,$T$ = 温度(K)。全部使用 SI 单位。

Combined Gas Law气体联合定律
$$\frac{P_1 V_1}{T_1} = \frac{P_2 V_2}{T_2}$$

Used when comparing the same sample of gas under two different sets of conditions.

用于比较同一份气体在两种不同条件下的状态。

Worked Example — Ideal Gas Equation例题 — 理想气体方程

Calculate the volume occupied by 0.250 mol of gas at 300 K and 150 kPa.

求 0.250 mol 气体在 300 K、150 kPa 下所占的体积。

Convert units to SI
$P$ = 150 kPa = 150,000 Pa. $T$ = 300 K. $n$ = 0.250 mol.
单位换算为 SI
$P$ = 150 kPa = 150,000 Pa;$T$ = 300 K;$n$ = 0.250 mol。
Apply PV = nRT
$$V = \frac{nRT}{P} = \frac{0.250 \times 8.314 \times 300}{150\,000}$$
$$V = \frac{623.55}{150\,000} = 4.16 \times 10^{-3}\;\text{m}^3 = 4.16\;\text{dm}^3$$
代入 PV = nRT
$$V = \frac{nRT}{P} = \frac{0.250 \times 8.314 \times 300}{150\,000}$$
$$V = \frac{623.55}{150\,000} = 4.16 \times 10^{-3}\;\text{m}^3 = 4.16\;\text{dm}^3$$
Under which conditions does a real gas behave most like an ideal gas?真实气体在哪种条件下最接近理想气体行为?
High temperature and low pressure高温且低压
Low temperature and high pressure低温且高压
Low temperature and low pressure低温且低压
High temperature and high pressure高温且高压
Correct! At high temperature, particles move fast and intermolecular forces are insignificant. At low pressure, particles are far apart and their volume is negligible. Both conditions match the ideal gas assumptions.正确!高温下粒子运动快,分子间作用力可忽略;低压下粒子距离远,其自身体积可忽略——两者都恰好符合理想气体的假设。
Ideal gas behavior requires conditions where intermolecular forces and particle volume are negligible: high $T$, low $P$. Answer: (A).理想气体行为要求分子间作用力与粒子自身体积均可忽略,即高 $T$、低 $P$。答案:(A)。
Going Deeper — Graham's Law and Rates of Diffusion Kinetic molecular theory predicts that at the same temperature, all gas particles have the same average kinetic energy ($\tfrac{1}{2}mv^2$) — but not the same speed. Lighter particles must move faster to have the same kinetic energy as heavier ones. This gives Graham's law: $\dfrac{\text{rate}_1}{\text{rate}_2} = \sqrt{\dfrac{M_2}{M_1}}$, where rate can mean either diffusion (spreading through another gas) or effusion (escaping through a tiny hole). A gas four times heavier diffuses at half the rate — not a quarter, because the relationship is a square root, not a direct ratio.
拓展 — 格拉汉姆定律与扩散速率 分子运动论预测:同一温度下,所有气体粒子的平均动能($\tfrac{1}{2}mv^2$)相同——但速率并不相同。较轻的粒子必须运动得更快,才能达到与较重粒子相同的动能。由此得到格拉汉姆定律Graham's law):$\dfrac{\text{rate}_1}{\text{rate}_2} = \sqrt{\dfrac{M_2}{M_1}}$,这里的速率可以是扩散(在另一种气体中散布)或泄漏(通过小孔逸出)。质量是另一气体 4 倍的气体,扩散速率是其一半——而不是四分之一,因为这是一个平方根关系,不是直接的比例关系。
Worked Example — Combined Gas Law例题 — 气体联合定律

A gas occupies 2.00 dm$^3$ at 300 K and 100 kPa. What volume will it occupy at 350 K and 120 kPa?

某气体在 300 K、100 kPa 下体积为 2.00 dm$^3$。在 350 K、120 kPa 下,它的体积是多少?

Step 1 — Identify the two states
State 1: $P_1 = 100$ kPa, $V_1 = 2.00$ dm$^3$, $T_1 = 300$ K. State 2: $P_2 = 120$ kPa, $T_2 = 350$ K, $V_2 = ?$
第 1 步 — 明确两个状态
状态 1:$P_1 = 100$ kPa,$V_1 = 2.00$ dm$^3$,$T_1 = 300$ K。状态 2:$P_2 = 120$ kPa,$T_2 = 350$ K,$V_2 = ?$
Step 2 — Apply the combined gas law
$$\frac{P_1V_1}{T_1} = \frac{P_2V_2}{T_2} \;\Longrightarrow\; V_2 = \frac{P_1V_1T_2}{T_1P_2}$$
第 2 步 — 代入气体联合定律
$$\frac{P_1V_1}{T_1} = \frac{P_2V_2}{T_2} \;\Longrightarrow\; V_2 = \frac{P_1V_1T_2}{T_1P_2}$$
Step 3 — Substitute (units for P and V can stay consistent as long as they match on both sides)
$$V_2 = \frac{(100)(2.00)(350)}{(300)(120)} = \frac{70\,000}{36\,000} = 1.94\;\text{dm}^3$$
Note: because $P$ and $V$ only ever appear as a product/ratio here, kPa and dm$^3$ can be used directly without converting to Pa and m$^3$ — unlike the single-state $PV=nRT$ equation, which requires strict SI units.
第 3 步 — 代入(只要两侧单位一致,P 和 V 可以保持原单位)
$$V_2 = \frac{(100)(2.00)(350)}{(300)(120)} = \frac{70\,000}{36\,000} = 1.94\;\text{dm}^3$$
注意:由于这里 $P$ 与 $V$ 始终只以乘积/比值的形式出现,kPa 和 dm$^3$ 可以直接使用,不必换算成 Pa 和 m$^3$——这与单一状态的 $PV=nRT$ 方程不同,后者必须严格使用 SI 单位。
Worked Example — Finding Molar Mass from Gas Density例题 — 由气体密度求摩尔质量

A 0.480 g sample of an unknown gas occupies 250 cm$^3$ at 298 K and 101 kPa. Find its molar mass.

某未知气体样品质量为 0.480 g,在 298 K、101 kPa 下占体积 250 cm$^3$。求其摩尔质量。

Step 1 — Rearrange PV = nRT to find n, converting to SI first
$$n = \frac{PV}{RT} = \frac{(101\,000)(250\times10^{-6})}{(8.314)(298)} = \frac{25.25}{2477.6} = 0.01019\;\text{mol}$$
第 1 步 — 先换算为 SI 单位,再由 PV = nRT 解出 n
$$n = \frac{PV}{RT} = \frac{(101\,000)(250\times10^{-6})}{(8.314)(298)} = \frac{25.25}{2477.6} = 0.01019\;\text{mol}$$
Step 2 — Apply M = m/n
$$M = \frac{m}{n} = \frac{0.480}{0.01019} = 47.1\;\text{g mol}^{-1}$$
This value is close to the molar mass of $\text{NO}_2$ or $\text{O}_3$ (both $\approx 46$–48 g mol$^{-1}$) — identifying the actual gas would need a second clue, such as its odor or color, but the calculation itself only ever needs mass, and the three PV=nRT variables.
第 2 步 — 代入 M = m/n
$$M = \frac{m}{n} = \frac{0.480}{0.01019} = 47.1\;\text{g mol}^{-1}$$
这个数值接近 $\text{NO}_2$ 或 $\text{O}_3$ 的摩尔质量(两者都约为 46–48 g mol$^{-1}$)——要确定具体是哪种气体,还需要第二条线索(如气味或颜色),但计算本身只需要质量,以及 PV=nRT 中的其余三个变量。

Exam Strategy考试策略

Paper 1 (Multiple Choice)Paper 1(Multiple Choice)

Know the subatomic particle table cold. For electron configurations, watch for ions (remove 4s before 3d for transition metals) and the Cr/Cu exceptions. Mole calculations are frequent — practise converting between mass, moles, particles, and concentration quickly.

亚原子粒子表必须背得滚瓜烂熟。电子构型题留意离子(过渡金属先失 4s 再失 3d),以及 Cr / Cu 两个例外。摩尔计算高频出现——练习快速在质量、物质的量、粒子数与浓度间互换。

Paper 2 (Extended Response)Paper 2(Extended Response)

Show all working in mole calculations: write the formula, substitute, and solve with units. For gas calculations, always convert to SI units before applying $PV = nRT$. Empirical formula questions: set up a clear table showing element, mass, moles, and ratio.

摩尔计算题写清全过程:先写公式,再代入数值,最后带单位求解。气体题在使用 $PV = nRT$ 之前先把全部数值换成 SI 单位。求实验式时列出清晰的"元素—质量—摩尔数—比"表。

Data BookletData Booklet

Key items to locate quickly: relative atomic masses (periodic table), Avogadro constant, molar gas volume at STP, gas constant $R$, the equations $n = m/M$, $n = CV$, $PV = nRT$, and the combined gas law.

数据手册中必须能快速定位:相对原子质量(周期表)、阿伏伽德罗常数、STP 下的摩尔气体体积、气体常数 $R$,以及 $n = m/M$、$n = CV$、$PV = nRT$ 和联合气体定律。


Common Mistakes常见错误

Mistake 1 — Forgetting Unit Conversions for PV=nRT $P$ must be in Pa (not kPa), $V$ must be in m$^3$ (not dm$^3$ or cm$^3$). 1 kPa = 1000 Pa. 1 dm$^3$ = 10$^{-3}$ m$^3$. Most errors in gas calculations come from mismatched units.
错误 1 — 忘记 PV=nRT 的单位换算 $P$ 必须用 Pa(不是 kPa),$V$ 必须用 m$^3$(不是 dm$^3$ 或 cm$^3$)。1 kPa = 1000 Pa;1 dm$^3$ = 10$^{-3}$ m$^3$。气体计算题大部分错误都源于单位不一致。
Mistake 2 — Removing 3d Electrons First When Forming Ions When transition metals form cations, the 4s electrons are lost before 3d electrons. Fe loses its two 4s electrons first to become Fe$^{2+}$: [Ar] 3d$^6$, not [Ar] 4s$^2$ 3d$^4$.
错误 2 — 形成阳离子时先失去 3d 电子 过渡金属形成阳离子时,先失 4s 电子、再失 3d 电子。Fe 先失去 2 个 4s 电子,形成 Fe$^{2+}$:[Ar] 3d$^6$,而不是 [Ar] 4s$^2$ 3d$^4$。
Mistake 3 — Confusing $A_r$ and $M$ Relative atomic mass ($A_r$) and relative formula mass ($M_r$) have no units. Molar mass ($M$) has units of g mol$^{-1}$. Numerically they are the same, but examiners penalize missing or incorrect units.
错误 3 — 混淆 $A_r$ 与 $M$ 相对原子质量($A_r$)与相对式量($M_r$)无单位;摩尔质量($M$)单位为 g mol$^{-1}$。三者数值相同,但漏写或写错单位会被考官扣分。
Mistake 4 — Using Celsius in Gas Calculations Temperature must always be in Kelvin for $PV = nRT$ and the combined gas law. Add 273 to convert from Celsius. Using Celsius gives wildly wrong answers (and zero marks).
错误 4 — 气体计算中使用摄氏度 $PV = nRT$ 与气体联合定律中的温度必须用开尔文(K)。摄氏度加 273 即得。直接用摄氏度会算出离谱的答案,得 0 分。
Mistake 5 — Rounding Intermediate Mole Ratios Too Early In empirical formula problems, dividing by the smallest mole value often gives numbers like 1.98 or 2.99 rather than exact integers. Students sometimes round these to whole numbers too early (before checking whether they're actually close to a simple fraction like 1.5 or 2.5), producing a formula with the wrong ratio. Always carry at least 2-3 decimal places through the division step, and if a ratio is close to $x.5$, multiply the whole set by 2 rather than rounding it away.
错误 5 — 中间摩尔比过早四舍五入 在求实验式时,除以最小摩尔数后常会得到 1.98 或 2.99 这类数值,而非整数。学生有时会过早把这些数值四舍五入为整数(还没检查它们是否其实接近 1.5 或 2.5 这类简单分数),从而得到比例错误的化学式。除法步骤中至少要保留 2–3 位小数,若某个比值接近 $x.5$,应把整组数值都乘以 2,而不是直接四舍五入抹掉。

Flashcards闪卡

Click a card to flip it.点击卡片翻面。

What are isotopes?什么是同位素(isotope)?
Atoms of the same element with different numbers of neutrons (same $Z$, different $A$).同种元素、中子数不同的原子($Z$ 相同、$A$ 不同)。
Maximum electrons in energy level $n$?第 $n$ 主能级最多容纳几个电子?
$2n^2$. So: $n$=1 holds 2, $n$=2 holds 8, $n$=3 holds 18, $n$=4 holds 32.$2n^2$。即:$n$=1 容 2 个、$n$=2 容 8 个、$n$=3 容 18 个、$n$=4 容 32 个。
State Avogadro's law叙述阿伏伽德罗定律
Equal volumes of all gases at the same $T$ and $P$ contain equal numbers of molecules.同 $T$ 同 $P$ 下,任何气体的等体积含有等数量的分子。
Electron config of Cr?Cr 的电子构型?
[Ar] 3d$^5$ 4s$^1$ (exception — not 3d$^4$ 4s$^2$). Half-filled d-sublevel is more stable.[Ar] 3d$^5$ 4s$^1$(例外,不是 3d$^4$ 4s$^2$)。d 亚层半充满更稳定。
When do real gases deviate most from ideal?真实气体在何条件下偏离理想气体最严重?
At low temperature and high pressure. Intermolecular forces and particle volume become significant.低温、高压。此时分子间作用力与粒子自身体积都不可忽略。
What is the molar volume at STP?STP 下的摩尔体积是?
22.7 dm$^3$ mol$^{-1}$ at 273.15 K and 100 kPa.在 273.15 K、100 kPa 下为 22.7 dm$^3$ mol$^{-1}$。
Empirical vs. molecular formula?实验式与分子式的区别?
Empirical = simplest whole-number ratio. Molecular = actual number of atoms. E.g., CH$_2$O vs. C$_6$H$_{12}$O$_6$.实验式 = 最简整数比;分子式 = 真实原子数。例:CH$_2$O 对应 C$_6$H$_{12}$O$_6$。
What happens to temperature during a phase change?物态变化过程中温度如何变化?
Temperature remains constant. Added energy overcomes intermolecular forces rather than increasing kinetic energy.温度保持不变。吸收的能量用于克服分子间作用力,而非增加动能。

Unit Quiz单元测验

1. Which separation technique is most appropriate for separating a dissolved solid from a solution?1. 从溶液中分离已溶解的固体,最合适的分离方法是?
Filtration过滤(filtration)
Chromatography色谱(chromatography)
Evaporation蒸发(evaporation)
Distillation蒸馏(distillation)
Correct! Evaporation removes the solvent (water), leaving the dissolved solid behind. Filtration separates insoluble solids, not dissolved ones.正确!蒸发可去除溶剂(水),留下溶质固体。过滤只能分离不溶性固体,对已溶解的固体无效。
A dissolved solid passes through filter paper. Evaporation removes the water, leaving the solid. Answer: (C).已溶解的固体会随溶液穿过滤纸。蒸发掉水后即可得到固体。答案:(C)。
2. What is the electron configuration of V$^{3+}$ (Z=23)?2. V$^{3+}$(Z=23)的电子构型是?
[Ar] 3d$^2$ 4s$^2$ minus 3 from 4s and 3d[Ar] 3d$^2$ 4s$^2$ 然后从 4s 与 3d 各失去若干
[Ar] 3d$^2$
[Ar] 3d$^3$ 4s$^2$ minus 3 from 3d[Ar] 3d$^3$ 4s$^2$ 仅从 3d 失去 3 个
[Ar] 4s$^2$ 3d$^0$
Correct! V is [Ar] 3d$^3$ 4s$^2$. Removing 3 electrons: 2 from 4s first, then 1 from 3d, giving [Ar] 3d$^2$.正确!V 的电子构型为 [Ar] 3d$^3$ 4s$^2$。失去 3 个电子时,先失 2 个 4s,再失 1 个 3d,剩 [Ar] 3d$^2$。
V = [Ar] 3d$^3$ 4s$^2$. Remove 4s electrons first (2), then 1 from 3d: V$^{3+}$ = [Ar] 3d$^2$. Answer: (B).V = [Ar] 3d$^3$ 4s$^2$。先失 4s(2 个),再失 3d(1 个):V$^{3+}$ = [Ar] 3d$^2$。答案:(B)。
3. What volume does 0.100 mol of an ideal gas occupy at STP (molar volume = 22.7 dm$^3$ mol$^{-1}$)?3. 在 STP(摩尔体积 = 22.7 dm$^3$ mol$^{-1}$)下,0.100 mol 理想气体占多大体积?
$0.227$ dm$^3$
$22.7$ dm$^3$
$227$ dm$^3$
$2.27$ dm$^3$
Correct! $V = n \times V_m = 0.100 \times 22.7 = 2.27$ dm$^3$.正确!$V = n \times V_m = 0.100 \times 22.7 = 2.27$ dm$^3$。
$V = n \times V_m = 0.100 \times 22.7 = 2.27$ dm$^3$. Answer: (D).$V = n \times V_m = 0.100 \times 22.7 = 2.27$ dm$^3$。答案:(D)。