The only procedural requirements that you can require employees to adhere to are the ‘notification requirements’. The notification requirements require that employees:
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tell their employer as soon as reasonably practicable of their need to take time off for a dependant, and
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tell their employer, wherever possible, how long they expect to be absent for
Bear in mind that, in some circumstances, it won’t be reasonably practicable for an employee to inform their employer of their absence before leaving work (eg in the case of a time-sensitive medical emergency involving a dependant). This is acceptable under the notification requirements, and employees should not be subjected to detriment for doing this.
You may ask employees to follow other steps when requesting time off for dependants, but you cannot make them comply (eg by subjecting them to detriment if they don’t comply or by denying them time off for dependants). Such steps could include, for example, ringing their line manager or requesting time off via an online HR portal.