Qualitative Chemical Analysis

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Questions and Answers

Qualitative chemical analysis primarily focuses on what aspect of a sample?

  • Calculating the energy released during chemical reactions.
  • Measuring the volume of each substance present.
  • Determining the exact mass of each element.
  • Identifying the components, such as ions, atoms, or molecules. (correct)

Which factor most directly dictates whether a method is classified as macro, semi-micro, micro, or ultramicro in qualitative analysis?

  • The type of equipment used.
  • The quantity of substance used in the analysis. (correct)
  • The temperature at which the reaction is performed.
  • The volume of solvent.

What term describes the transformation of an analyte into a different compound for analysis?

  • Titration.
  • Analytical reaction. (correct)
  • Sublimation.
  • Distillation.

In 'dry path' analytical reactions, in what state are the analyte and reagent?

<p>Both are in a solid state. (A)</p> Signup and view all the answers

What is the key characteristic of 'wet path' analytical reactions?

<p>The sample is dissolved in a solvent. (C)</p> Signup and view all the answers

What observable change indicates a chemical reaction has occurred in wet path analysis?

<p>Visible external changes. (A)</p> Signup and view all the answers

What term describes a reaction where only one substance is detected, even in a mixture?

<p>Specific reaction. (A)</p> Signup and view all the answers

What factor may be altered to influence the selectivity of a chemical reaction?

<p>The pH and temperature of the reaction. (D)</p> Signup and view all the answers

What term refers to the smallest amount of a substance detectable by an analytical reaction?

<p>Sensitivity. (C)</p> Signup and view all the answers

In systematic qualitative analysis, what is the purpose of using group reagents?

<p>To selectively precipitate, dissolve, or separate ions into groups. (A)</p> Signup and view all the answers

What is the main principle behind the Fresenius scheme for cation analysis?

<p>Differences in solubility of chlorides, sulfides, hydroxides, and carbonates. (B)</p> Signup and view all the answers

What application has classic qualitative analysis had in pharmacy?

<p>Identifying ions of interest. (B)</p> Signup and view all the answers

What resource provides reaction details for identifying chemicals within the European Pharmacopoeia?

<p>Reaction for Identification of ions and functional group (2.3.1) (D)</p> Signup and view all the answers

Which of the following ions belong to the first analytical group of cations?

<p>$Ag^+$, $Hg_2^{2+}$, $Pb^{2+}$ (B)</p> Signup and view all the answers

What is the common characteristic of the chlorides formed by the first analytical group cations?

<p>They are difficult to dissolve in water. (A)</p> Signup and view all the answers

Identify the precipitate which occurs when $Ag^+$ reacts with $Cl^-$?

<p>AgCl (D)</p> Signup and view all the answers

What is the color of precipitate when $Pb^{2+}$ reacts with $I^−$?

<p>Yellow. (C)</p> Signup and view all the answers

What conditions define the second analytical group of cations?

<p>React with thioacetamide to precipitate sulfides in an acidic medium. (B)</p> Signup and view all the answers

What reagent is used to precipitate sulfides of the second analytical group cations?

<p>$CH_3CSNH_2$ (D)</p> Signup and view all the answers

What characterizes the second subgroup of the second analytical cation group?

<p>Their sulfides are soluble in bases, forming tiosoli. (B)</p> Signup and view all the answers

What precipitate is formed when $Bi^{3+}$ reacts with thioacetamide ($CH_3CSNH_2$)?

<p>$Bi_2S_3$ (D)</p> Signup and view all the answers

In the third analytical group, what reagent precipitates the cations?

<p>Ammonia in the presence of ammonium chloride. (A)</p> Signup and view all the answers

What color is the complex formed when $Fe^{3+}$ reacts with thiocyanate ions ($SCN^−$)?

<p>Red. (A)</p> Signup and view all the answers

What is the precipitate formed between $Zn^{2+}$ and alkaline hydroxides?

<p>$Zn(OH)_2$ (C)</p> Signup and view all the answers

What reagent precipitates cations from the fifth analytical group?

<p>Ammonium carbonate in an ammoniacal medium. (A)</p> Signup and view all the answers

Which reagent identifies $K^+$ in the sixth analytical group?

<p>Sodium hexanitrocobaltate (III) (C)</p> Signup and view all the answers

What reagent is used to identify $Mg^{2+}$?

<p>Sodium hydrogen phosphate in the presence of ammonia and ammonium chloride (C)</p> Signup and view all the answers

What precipitate results from the reaction of $Ag^+$ with $Br^−$?

<p>AgBr (B)</p> Signup and view all the answers

What is observed when chloride is reacted with silver nitrate ($AgNO_3$)?

<p>A white precipitate (A)</p> Signup and view all the answers

What results from $CO_3^{2−}$ reacting with $H^+$?

<p>Evolution of $CO_2$ gas (B)</p> Signup and view all the answers

Што е примарна цел на квалитативната хемиска анализа?

<p>Идентификација на елементарните единки во примерокот. (C)</p> Signup and view all the answers

Методите на квалитативна анализа се базираат исклучиво на нуклеарни реакции.

<p>False (B)</p> Signup and view all the answers

Како се нарекува реагенсот кој предизвикува промена во аналитичка реакција?

<p>аналитички реагенс</p> Signup and view all the answers

Анализа во која примерокот се раствора во вода се нарекува анализа по ______ пат.

<p>мокар</p> Signup and view all the answers

Поврзете ги аналитичките реакции со нивните описи:

<p>Групна реакција = Реакција карактеристична за голем број јони. Селективна реакција = Реакција карактеристична за неколку јони. Специфична реакција = Реакција карактеристична само за еден јон.</p> Signup and view all the answers

Што значи осетливост на аналитичка реакција?

<p>Најмала концентрација на аналит која може да се докаже. (A)</p> Signup and view all the answers

Систематската квалитативна анализа се базира на примена на еден реагенс за сите јони.

<p>False (B)</p> Signup and view all the answers

Кој научник е познат по шемата за систематска анализа на катјони од 1841 година?

<p>Fresenius</p> Signup and view all the answers

Европската фармакопеја содржи поглавје за реакции за идентификација на јони и ____ групи.

<p>функционални</p> Signup and view all the answers

Поврзете ги катјоните од првата аналитичка група со нивните реакции со HCl:

<p>Ag+ = AgCl Hg2+2 = Hg2Cl2 Pb2+ = PbCl2</p> Signup and view all the answers

Кој реагенс се користи за таложење на сулфиди во кисела средина во втората аналитичка група?

<p>CH₃CSNH₂ (тиоацетамид) (B)</p> Signup and view all the answers

Сите сулфиди од втората аналитичка група се растворливи во бази.

<p>False (B)</p> Signup and view all the answers

Каков талог се формира при реакција на Bi3+ со тиоацетамид?

<p>црн или темно кафеав</p> Signup and view all the answers

Al3+, Fe3+ и Cr3+ се таложат како ______ во третата аналитичка група.

<p>хидроксиди</p> Signup and view all the answers

Поврзете ги реакциите со нивниот резултат за Fe3+:

<p>Со алкални хидроксиди = Црвено-кафеав талог Со калиум тиоцијанат = Црвено обоен комплекс Со калиум хексацијаноферат (II) = Син талог</p> Signup and view all the answers

Кои јони спаѓаат во четвртата аналитичка група?

<p>Ni²⁺, Co²⁺, Mn²⁺, Zn²⁺ (D)</p> Signup and view all the answers

Zn(OH)₂ е растворлив во алкални хидроксиди.

<p>False (B)</p> Signup and view all the answers

Во која средина се таложат катјоните од петтата аналитичка група со амониум карбонат?

<p>амонијачна</p> Signup and view all the answers

K+, Na+, Li+, NH₄⁺ и Mg²⁺ припаѓаат на ______ аналитичка група.

<p>шестата</p> Signup and view all the answers

Со што реагира NH₄⁺ во присуство на KOH (Nessler-ов реагенс) за да даде жолт талог?

<p>K₂[HgI₄] (D)</p> Signup and view all the answers

MgNH₄PO₄ е талог кој се формира во облик на коцки.

<p>False (B)</p> Signup and view all the answers

Што се користи како реагенс за таложење на хлориди?

<p>сребро нитрат</p> Signup and view all the answers

Реакцијата на сребро нитрат со бромид дава ______ жолт талог.

<p>светло</p> Signup and view all the answers

Поврзете ги халогените со бојата на хлороформскиот раствор по реакцијата со хлорна вода:

<p>Бром = Жолта или кафена Јод = Виолетова</p> Signup and view all the answers

CH₃COO⁻ реагира со разредена сулфурна киселина за да даде:

<p>Мирис на оцетна киселина (B)</p> Signup and view all the answers

Реакцијата на CH₃COO⁻ со концентрирана сулфурна киселина и етанол дава пријатен мирис на распаѓање.

<p>False (B)</p> Signup and view all the answers

Што се ослободува при реакција на карбонати со киселина?

<p>јаглерод диоксид</p> Signup and view all the answers

Реакцијата на сребро нитрат со фосфат дава ______ талог.

<p>жолт</p> Signup and view all the answers

Каков талог се формира кога сулфат реагира со бариум хлорид?

<p>Бел (A)</p> Signup and view all the answers

Количината на супстанција во макро анализа е секогаш помала од 1 mg.

<p>False (B)</p> Signup and view all the answers

Каков талог се формира при реакција со калиум дихромат со Hg₂²⁺?

<p>црвен</p> Signup and view all the answers

Сулфидите од првата подгрупа во втората аналитичка група се ______ во бази.

<p>нерастворливи</p> Signup and view all the answers

Поврзете ги аналитичките групи со нивните групни реагенси:

<p>Прва аналитичка група = HCl Втора аналитичка група = CH₃CSNH₂ Трета аналитичка група = NH₃</p> Signup and view all the answers

Што е тоа тиосол?

<p>Сулфидна сол која се раствора во бази. (A)</p> Signup and view all the answers

Најпознатата шема за разделување на катјоните е онаа на Бунзен.

<p>False (B)</p> Signup and view all the answers

Која боја се добива при реакција на Fe³⁺ со калиум тиоцијанат?

<p>црвена</p> Signup and view all the answers

Каков талог се формира при реакција на Pb²⁺ со калиум дихромат?

<p>Жолт. (B)</p> Signup and view all the answers

При реакција на СО3²⁻ со 2H+ се ослободува ______ во форма на меурчиња.

<p>CO₂</p> Signup and view all the answers

Flashcards

Qualitative Analysis

Identification of elemental units (ions, atoms, molecules) in a sample.

Analytical Reaction

A reaction used to convert an analyte. The reagent causing the change.

Dry Path Analysis

Reactions where the analyte is in solid form, with the reagent also being a solid.

Wet Path Analysis

Reactions where the sample is dissolved in water or another solvent.

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Reaction Specificity

A reaction given by multiple, several, or just one ion.

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Specific Reaction

When a reagent reacts solely with one ion under specific conditions.

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Reaction Sensitivity

The smallest amount of analyte detectable by the analytical reaction.

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Systematic Qualitative Analysis

Separating ions into groups based on similar properties.

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Fresenius Scheme

Analytical scheme for cation analysis that is based on solubility.

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Pharmacopoeia Reactions

Reactions for the identification of ions and functional groups.

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First Analytical Group

Ag+, Hg22+, Pb2+ form insoluble chloride salts with HCl.

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Second Analytical Group

Hg2+, Cu2+, Cd2+, Bi3+, Pb2+, Sn2+ form sulfides in acidic conditions.

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Second Analytical Group Reagent

Group reagent thioacetamide forms sulfides in acidic medium.

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Third Analytical Group

Al3+, Fe3+, Cr3+ precipitate as hydroxides with NH3 at pH 9.

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Fourth Analytical Group

Ni2+, Co2+, Mn2+, Zn2+ form sulfides with thioacetamide in ammonia.

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Fifth Analytical Group

Ba2+, Sr2+, Ca2+ precipitate as carbonates in ammonia with ammonium carbonate.

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Sixth Analytical Group

K+, Na+, Li+, NH4+, Mg2+ lack a group reagent.

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Reaction of Silver with Chloride

AgCl is created.

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Anion Analysis

Anionic groups identified, split into 6 groups.

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Carbonate with Acid

H2CO3 formation leads to CO2 gas bubbles.

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Potassium with Sodium Hexanitrocobaltate

K2Na[Co(NO2)6] creates a yellow precipitate.

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Што се анализира кај квалитативната анализа?

Елементите (јоните, атомите, молекулите) кои го сочинуваат примерокот се идентификуваат.

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Анализа по сув пат

Супстанцијата за анализа е во цврста форма, а реагенсот исто така во цврста форма.

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Реакции на обојување на пламен

Реакцијата на обојување каде што солите на некои метали го обојуваат пламенот во карактеристична боја.

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Формирање обоени перли

Кога солите на определни метали се топат со Na2B4O7 · 10H2O или NaNH4HPO4 · x 4H2O.

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Топење на непозната супстанција

Непозната супстанција се топи со различни смеси.

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Анализа по мокар пат

Примерокот се раствора во вода или друг растворувач, предизвикувајќи видливи промени.

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Појава на боја

Феноменот кога се појавува нова боја при реакција.

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Исчезнување на боја

Феноменот кога постоечка боја исчезнува.

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Формирање на талог

Се формира цврста супстанција (талог).

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Издвојување на гас со карактеристична миризба

Ослободување гас со карактеристичен мирис.

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Издвојување на гас со карактеристична боја

Ослободување гас со специфична боја.

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Реакција на прва аналитичка група со HCl

Реакција каде што групниот реагенс HCl формира тешко растворливи хлориди.

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Прва подгрупа на втора аналитичка група

Сулфидите стануваат нерастворливи во бази.

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Втора подгрупа на втора аналитичка група

Сулфидни соли кои се раствораат во бази и образуваат тиосоли.

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Реакција на Bi3+ со тиоацетамид

При рН=0,5 или со загревање формира црн или темно кафеав талог.

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Реакција на Sb3+ со тиоацетамид

При рН=0,5 или со загревање формира портокалов талог.

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Реакција на Al3+ со хидроксиди

Со алкални хидроксиди (KOH и NaOH) дава бел пифтиест талог.

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Реакција на Fe3+ со хидроксиди

Со алкалните хидроксиди (KOH и NaOH), се добива црвено-кафеав талог.

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Реакција на Fe3+ со тиоцијанат

Образува црвено обоен комплекс.

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Реакција на Mg2+ со хидрогенфосфат

Во присуство на амонијак и амониум хлорид се добива бел кристален талог во форма на ѕвездици.

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Карактеристични реакции за Br

Cl2 + 2Br → IВr2 + KCl хлороформскиот раствор ќе се обои со жолта или кафена боја од издвоениот бром

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Study Notes

  • Qualitative chemical analysis involves identifying the elemental units (ions, atoms, molecules) of a sample

  • Analytical methods rely on observing chemical reactions or physical phenomena during analysis

Substance Quantity for Analysis

  • Macro: 0.5-1 g substance in 20-50 ml solution
  • Semimicro: 50 mg substance in 1 ml solution
  • Micro: 5-10 mg substance in 0.1 ml solution
  • Ultramicro: Less than 1 mg of substance

Types of Analytical Reactions

  • Analytical reaction: Transformation of an analyte into another compound
  • Analytical reagent: The reagent causing this transformation
  • Dry path analysis: Involves analyte and reagent in solid form

Dry path analysis methods

  • Flame coloring reactions: Metal salts color the flame distinctively
  • Colored pearl formation: Certain metal salts fuse with specific compounds, forming colored pearls like Na2B4O7 x 10H2O or NaNH4HPO4 x 4H2O
  • Melting with mixtures: Involves melting an unknown substance with mixtures such as Na2CO3 and K2CO3, or Na2CO3 and KNO

Wet path analysis

  • Sample dissolves in water or another solvent.
  • Visible changes indicate chemical reaction progress, examples of which, outlined below:
  • Color appearance.
  • Color disappearance.
  • Precipitate formation.
  • Gas evolution.
  • Distinct odor.
  • Characteristic color.

Specificity and Sensitivity of Analytical Reactions

  • Reactions can be given by multiple ions, several ions, or a single ion
  • Group reactions: Characteristic of many ions
  • Selective reactions: Characteristic of a few ions; selectivity can be adjusted by altering reaction conditions (pH, temperature)
  • Specific reactions: Characteristic of one ion exclusively under specific conditions

Sensitivity

  • Defines the lowest analyte concentration detectable through the analytical reaction
  • Must be validated via blind trial

Systematic Qualitative Analysis

  • Follows a series of group and/or selective reagents
  • Ions precipitate, dissolve, and separate into groups based on shared properties
  • Consists of separation and identification methods

Ion Separation Schemes

  • Various
  • The Fresenuis scheme has been used since 1841.
  • It relies on the differing solubilities of chlorides, sulfides, hydroxides, and carbonates of the cations being tested

Importance of Classical Analysis

Classical cation and anion qualitative analysis has pharmaceutical uses for identifying ions of interest.

  • European Pharmacopoeia's general chapter contains reactions for identifying ions and functional groups in pharmaceutical substances

First Analytical Group

  • Includes Ag+, Hg₂²+, Pb²+, which form sparingly soluble chloride salts with HCl

Aqueous Reactions for Ag+

  • With HCl: Ag+ + Cl- ⇋ AgCl (white precipitate)
  • With iodides: Ag+ + I- ⇋ AgI (pale yellow precipitate)
  • With potassium dichromate: 2Ag+ + Cr₂O₄²- ⇋ Ag₂Cr₂O₇ (red-brown precipitate)

Aqueous Reactions for Pb²+

  • With HCl: Pb²+ + 2Cl- ⇋ PbCl₂ (white precipitate)
  • With iodides: Pb²+ + 2I- ⇋ PbI₂ (yellow precipitate)
  • With potassium dichromate: Pb²+ + CrO₄²- ⇋ PbCrO₄ (yellow precipitate)

Aqueous Reactions for Hg₂+

  • With HCl: Hg₂²+ + 2Cl- ⇋ Hg₂Cl₂ (white precipitate)
  • With iodides: Hg₂²+ + 2I- ⇋ Hg₂I₂ (green precipitate)
  • With potassium dichromate: Hg₂²+ + CrO₄²- ⇋ Hg₂CrO₄ (red precipitate)

Second Analytical Group

  • Features cations reacting with thioacetamide (CH₃CSNH₂) to precipitate sulfides or sulfide compounds in acidic conditions
  • Divided into two subgroups

First Subgroup

  • Contains Hg²+, Cu²+, Cd²+, Bi³+, Pb²+, Sn²+; their sulfides are insoluble in bases

Second Subgroup

  • Contains Hg²+, As³+, As⁵+, Sb³+, Sb⁵+, Sn⁴+ where sulfide salts dissolve in bases, forming thiosols

Aqueous Reactions for Bi³+

  • With thioacetamide (CH₃CSNH₂) at pH 0.5 and heating: 2Bi³+ + 3S²- ⇋ Bi₂S₃ (black or dark brown precipitate)

Aqueous Reactions for Sb³+

  • With thioacetamide (CH₃CSNH₂) at pH 0.5 and heating: 2Sb³+ + 3S²- ⇋ Sb₂S₃ (orange precipitate)

Third Analytical Group

  • Features Al³+, Fe³+, Cr³+, which precipitate as hydroxides with ammonia (NH₃) and ammonium chloride (pH 9).

Aqueous Reactions for Al³+

  • With alkaline hydroxides (KOH and NaOH): Al³+ + 3OH- ⇋ Al(OH)₃ (white, gelatinous precipitate)

Aqueous Reactions for Fe³+

  • With alkaline hydroxides (KOH and NaOH): Fe³+ + 3OH- ⇋ Fe(OH)₃ (red-brown precipitate)
  • With potassium or ammonium thiocyanate (NH₄SCN or KSCN): Fe³+ + SCN- ⇋ [Fe(SCN)]²+ (red complex)
  • With potassium hexacyanoferrate(II) (K4[Fe(CN)6]) in slightly acidic conditions: 4Fe³+ + 3[Fe(CN)6]⁴- → Fe₄[Fe(CN)6]₃ (blue precipitate, Prussian blue)

Fourth Analytical Group

  • Contains Ni²+, Co²+, Mn²+, Zn²+, which precipitate as sulfides with thioacetamide (CH₃CSNH₂) in the presence of ammonia

Aqueous Reactions for Zn²+

  • With alkaline hydroxides: Zn²+ + 2OH- ⇋ Zn(OH)₂ (white precipitate)

Fifth Analytical Group

  • Features Ba²+, Sr²+, Ca²+, which precipitate as carbonates with ammonium carbonate in an ammoniacal solution

Aqueous Reactions for Ca²+

  • With ammonium carbonate: Ca²+ + CO₃²- ⇋ CaCO₃ (white precipitate)
  • With ammonium oxalate: Ca²+ + C₂O₄²- ⇋ CaC₂O₄ (white precipitate)

Sixth Analytical Group

  • Includes K+, Na+, Li+, NH₄+, Mg²+, lacking a group reagent

Aqueous Reactions for K+

  • With sodium hexanitrocobaltate(III) (Na₃[Co(NO₂)6]): 2K+ + Na+ + [Co(NO₂)6]³- ⇋ K₂Na[Co(NO₂)6] (yellow precipitate)

Aqueous Reactions for NH₄+

  • With Nessler's reagent, a K₂[HgI₄] solution in KOH: NH₄+ + 2[HgI₄]²- + 4OH- ⇋ [O0Hg0NH₂]I + 7I + 3H₂O (yellow precipitate or opalescence)

Aqueous Reactions for Mg²+

  • With sodium hydrogen phosphate in ammonia and ammonium chloride: Mg²+ + HPO₄²- + NH₃ + H₂O ⇋ MgNH₄PO₄ + H₂O (white crystalline precipitate in star shapes)

Anions (Bunsen's Division)

  • Group I: Cl–, Br–, I–, CN–, SCN–, [Fe(CN)6]4–, [Fe(CN)6]3–
  • Group II: S2–, NO2–, CH3COO–
  • Group III: CO32–, SO32–, BO2–, C2O42–, H4C4O62–
  • Group IV: PO43–, AsO43–, AsO33–, CrO42–, S2O32–
  • Group V: NO3–, MnO4–
  • Group VI: SO42–, F–

First Analytical Group

  • Characterized by reactions for each ion

Reactions specific to Cl¯

  • With silver nitrate: Ag+ + Cl¯ ⇋ AgCl (white precipitate)

Reactions specific to Br¯

  • With silver nitrate: Ag+ + Br¯ ⇋ AgBr (pale yellow precipitate)
  • With chlorine water, sulfuric acid, and chloroform: Cl₂ + 2Br ⇋ IBr₂ + 2Cl⁻ (chloroform layer turns yellow or brown from liberated bromine)

Reactions specific to I

  • With silver nitrate: Ag+ + I- ⇋ AgI (yellow precipitate)
  • With chlorine water, sulfuric acid, and chloroform: Cl₂ + 2I- ⇋ I₂ + 2Cl (chloroform layer turns violet from liberated iodine)

Second Analytical Group (Anions)

  • Characterized by reactions of acetate ion (CH₃COO-)

Specific Reactions for CH₃COO-

  • With dilute sulfuric acid: 2CH₃COONa + H₂SO₄ ⇋ 2CH₃COOH + Na₂SO₄ (acetic acid odor)
  • With concentrated sulfuric acid, ethanol, and heating: 2CH₃COONa + H₂SO₄ → 2CH₃COOH + Na₂SO₄; 2CH₃COOH + C₂H₅OH → CH₃COOC₂H₅ + H₂O (acetic acid converts to ethyl acetate, a pleasant fruity odor)

Analytical Groups 3-6 (Anions)

  • Characterized by reactions for carbonate and phosphate ions.

Specific Reactions for CO₃²- (Third Group)

  • With acid: CO₃²- + 2H+ ⇋ H₂CO₃ where H₂CO₃ releases CO₂ as bubbles

Specific Reactions for PO₄³- (Fourth Group)

  • With silver nitrate: 3Ag+ + PO₄³- ⇋ Ag₃PO₄ (yellow precipitate)

Reactions for NO₃ (Fifth Group)

  • With FeSO₄ and concentrated sulfuric acid produces : 3Fe²+ + NO₃ + 4H+ -> 3F6 + NO + 2H20.
  • The solution will have a the following occur: NO + Fe²+ + SO₄ -> [Fe(NO)SO₄] in (brown ring)

Specific Reactions for SO₄²- (Sixth Group)

  • With barium chloride: Ba²+ + SO₄²- ⇋ BaSO₄ (white precipitate)

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